Revision Notes Chemistry

1.
Atomic Structure and Periodic Table

Details of the three Sub-atomic (fundamental) Particles
Particle Position Relative Mass Relative Charge

Proton Nucleus 1 +1
Neutron Nucleus 1 0 There are various
Electron Orbitals 1/1800 -1 models for atomic
structure
An atom of Lithium (Li) can be represented as follows:
Mass Number 7 Li Atomic Symbol

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

compared to one twelfth of the mass of one atom of carbon-12
Isotopes have similar chemical properties because they have the same electronic structure.
They may have slightly varying physical properties because they have different masses.
DEFINITION: Relative atomic mass is the average mass of one atom

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

THE MASS SPECTROMETER

The mass spectrometer can be used to determine all the isotopes present in a sample of an element and
to therefore identify elements.
Calculating relative atomic mass
The relative atomic mass quoted on the periodic table is a weighted average of all the isotopes
Fig: spectra for

100 Magnesium from mass
spectrometer
80 78.70%
For each isotope the mass
% abundance
24Mg+
60 spectrometer can measure a m/z
40 (mass/charge ratio) and an abundance
25Mg+ 26Mg+
20 10.13% If asked to give the species for a peak

11.17% in a mass spectrum then give charge
and mass number e.g. 24Mg+
m/z
24 25 26
N Goalby chemrevise.org 1
Sometimes two electrons may be
R.A.M = Σ (isotopic mass x % abundance) removed from a particle forming a 2+
ion. 24Mg2+ with a 2+ charge would
100 have a m/z of 12
For above example of Mg

R.A.M = [(78.7 x 24) + (10.13 x 25) + (11.17 x 26)] /100 = 24.3 Use these equations to
work out the R.A.M
R.A.M = Σ (isotopic mass x relative abundance)
If relative abundance is used instead of
total relative abundance percentage abundance use this equation
Mass spectra for Cl2 and Br2

Cl has two isotopes Cl35 (75%) and Cl37(25%) Br has two isotopes Br79 (50%) and Br81(50%)
These lead to the following spectra caused by the diatomic molecules

Br79Br81 +
Br81Br79 +
Cl35Cl35 + relative
relative abundance
abundance Cl35Cl37 + Br79Br79 + Br81Br81 +
Cl37Cl37 +
70 72 74 m/z m/z
158 160 162
Measuring the Mr of a molecule Spectra for C4H10

If a molecule is put through a mass spectrometer it
will often break up and give a series of peaks caused Mass spectrum for butane
by the fragments. The peak with the largest m/z,
however, will be due to the complete molecule and 43
will be equal to the Mr of the molecule. This peak is Molecular ion
called the parent ion or molecular ion C4H10+
29
58
Uses of Mass spectrometers

• Mass spectrometers have been included in planetary space probes so that elements on other
planets can be identified. Elements on other planets can have a different composition of
isotopes.
• Drug testing in sport to identify chemicals in the blood and to identify breakdown products
from drugs in body
• quality control in pharmaceutical industry and to identify molecules from sample with
potential biological activity
• radioactive dating to determine age of fossils or human remains
Ionisation Energies
Definition :First ionisation energy Remember these
definitions very carefully
The first ionisation energy is the energy required when one mole of gaseous
atoms forms one mole of gaseous ions with a single positive charge
The equation for 1st ionisation
This is represented by the equation: H(g) H+ (g) + e- energy always follows the same
pattern.
It does not matter if the atom does
Always gaseous not normally form a +1 ion or is not
gaseous
Definition :Second ionisation energy
The second ionisation energy is the energy required when one mole of
gaseous ions with a single positive charge forms one mole of gaseous
ions with a double positive charge
This is represented by the equation: Ti+ (g) Ti2+(g) + e-

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

The patterns in successive ionisation energies for an element give us important
information about the electronic structure for that element.
Why are successive ionisation energies always larger?

The second ionisation energy of an element is always bigger than the first ionisation energy.
When the first electron is removed a positive ion is formed.
The ion increases the attraction on the remaining electrons and so the energy required to
remove the next electron is larger.
How are ionisation energies linked to electronic structure?
Explanation
Ionisation The fifth electron is in a inner
energy shell closer to the nucleus and
therefore attracted much more
Notice the big strongly by the nucleus than the
jump between 4 fourth electron.
and 5. It also does not have any
shielding by inner complete shells
1 2 3 4 5 6 of electron
No of electrons removed
Example: What group must this element be in? Here there is a big jump between the 2nd and 3rd
ionisations energies which means that this
1 2 3 4 5 element must be in group 2 of the periodic table
Ionisation 590 1150 4940 6480 8120 as the 3rd electron is removed from an electron
energy kJ mol-1 shell closer to the nucleus with less shielding and
so has a larger ionisation energy
The first Ionisation energy of the elements
The shape of the graph for periods two and
three is similar. A repeating pattern across a
Ionisation energy kJ mol-1
period is called periodicity.

2000
1500 The pattern in the first ionisation energy

gives us useful information about
1000 electronic structure
500
You need to carefully learn the
0 patterns
5 10 15 20
Atomic number
Q. Why has Helium the largest first ionisation energy?
A. Its first electron is in the first shell closest to the nucleus and has no
shielding effects from inner shells. He has a bigger first ionisation Many questions can be
energy than H as it has one more proton answered by application of
the 3 factors that control
Q. Why do first ionisation energies decrease down a group? ionisation energy
A. As one goes down a group, the outer electrons are found in shells
further from the nucleus and are more shielded so the attraction of
the nucleus becomes smaller
Q. Why is there a general increase in first ionisation energy across a period?
A. As one goes across a period , the number of protons increases making

the effective attraction of the nucleus greater. The electrons are being
added to the same shell which has the same shielding effect and the
electrons are pulled in closer to the nucleus.
Q. Why has Na a much lower first ionisation energy than Neon?
This is because Na will have its outer electron in a 3s shell further from
the nucleus and is more shielded. So Na’s outer electron is easier to
remove and has a lower ionisation energy.
Q. Why is there a small drop from Mg to Al?
Al is starting to fill a 3p sub shell, whereas Mg has its outer electrons in the 3s
sub shell. The electrons in the 3p subshell are slightly easier to remove because
the 3p electrons are higher in energy and are also slightly shielded by the 3s
electrons
Learn carefully the
explanations for
Q. Why is there a small drop from P to S?
these two small
With sulphur there are 4 electrons in the 3p sub shell and the 4th is starting to doubly drops as they are
fill the first 3p orbital. different to the
When the second electron is added to a 3p orbital there is a slight repulsion between usual factors
the two negatively charged electrons which makes the second electron easier to
remove.
3p 3p
3s 3s
Two electrons of opposite spin in
the same orbital
phosphorus 1s2 2s2 2p63s23p3
sulphur 1s2 2s2 2p63s23p4
Electronic Structure
Models of the atom
An early model of the atom was the Bohr model (GCSE model) (2 electrons in first shell, 8 in second etc.) with
electrons in spherical orbits. Early models of atomic structure predicted that atoms and ions with noble gas
electron arrangements should be stable.
The A-level model

Electrons are arranged on: Sub energy levels labelled s ,
p, d and f
Principle energy levels Split Orbitals which hold up
s holds up to 2 electrons Split
numbered 1,2,3,4.. into to 2 electrons of
p holds up to 6 electrons into
1 is closest to nucleus opposite spin
d holds up to 10 electrons
f holds up to 14 electrons
Shapes of orbitals
Orbitals represent the
Principle level 1 2 3 4 mathematical probabilities of
finding an electron at any point
within certain spatial
Sub-level distributions around the
1s 2s, 2p 3s, 3p, 3d 4s, 4p, 4d, 4f nucleus.
Each orbital has its own
approximate, three
An atom fills up the sub shells in order of increasing energy (note 3d is dimensional shape.
higher in energy than 4s and so gets filled after the 4s It is not possible to draw the
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p shape of orbitals precisely.
Writing electronic structure using letters and numbers •s sublevels are

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

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

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

orbitals, fill each orbital singly before starting
to pair up the electrons
2p
Electronic structure for ions

When a positive ion is formed electrons are lost When a negative ion is formed electrons are gained
Mg is 1s2 2s2 2p6 3s2 but Mg2+ is 1s2 2s2 2p6 O is 1s2 2s2 2p4 but O2- is 1s2 2s2 2p6
PERIODICITY
Classification of elements in s, p, d blocks
Elements are classified as s, p or d block, according

to which orbitals the highest energy electrons are in.
Period 2 = Li, Be, B, C, N, O, F, Ne

Period 3 = Na, Mg, Al, Si, P, S, Cl, Ar
Atomic radius 0.18
atomic radius (nm)

0.16
Atomic radii decrease as you move from left to right
0.14
across a period, because the increased number of 0.12
protons create more positive charge attraction for 0.1
electrons which are in the same shell with similar 0.08
shielding. 0.06
0.04
0.02
Exactly the same trend in period 2 0
Na Mg Al Si P S Cl Ar
1st ionisation energy

There is a general trend across is to increase. This is due to
1600
increasing number of protons as the electrons are being 1400
added to the same shell 1200
(kJ/mol)
1000
There is a small drop between Mg + Al. Mg has its outer 800
600
electrons in the 3s sub shell, whereas Al is starting to fill the
400
3p subshell. Al’s electron is slightly easier to remove
200
because the 3p electrons are higher in energy. 0
There is a small drop between phosphorous and sulphur.
Sulphur’s outer electron is being paired up with an another Exactly the same trend in period 2 with
electron in the same 3p orbital. drops between Be & B and N to O for
When the second electron is added to an orbital there is a same reasons- make sure change 3s
slight repulsion between the two negatively charged and 3p to 2s and 2p in explanation!
electrons which makes the second electron easier to remove.
Melting and boiling points

For Na, Mg, Al- Metallic bonding : strong bonding – gets 3000
stronger the more electrons there are in the outer shell that are
Melting and boiling
2500
released to the sea of electrons. A smaller positive centre also 2000
points (K)
makes the bonding stronger. High energy is needed to break

1500
bonds.
1000
Si is Macromolecular: many strong covalent bonds between
500
atoms high energy needed to break covalent bonds– very high
0
mp +bp
Cl2 (g), S8 (s), P4 (S)- simple Molecular : weak London forces
between molecules, so little energy is needed to break them – Similar trend in period 2
low mp+ bp Li,Be metallic bonding (high mp)
S8 has a higher mp than P4 because it has more electrons (S8 B,C macromolecular (very high mp)
=128)(P4=60) so has stronger London forces between N2,O2 molecular (gases! Low mp as
molecules small London Forces)
Ne monoatomic gas (very low mp)
Ar is monoatomic weak London Forces between atoms
N Goalby chemrevise.org
2. Bonding
Ionic Bonding
Metal atoms lose electrons to form +ve ions.
Non-metal atoms gain electrons to form -ve ions.
Mg goes from 1s2 2s2 2p63s2

to Mg2+ 1s2 2s2 2p6
O goes from 1s2 2s2 2p4 to

O2- 1s2 2s2 2p6
Ionic crystals have the structure of giant lattices of ions
An Ionic bond is the strong electrostatic force of attraction

between oppositely charged ions formed by electron transfer.
Ionic bonding is stronger and the melting points higher when the ions
are smaller and/ or have higher charges. E.g. MgO has a higher
melting point than NaCl as the ions involved (Mg2+ & O2- are smaller
and have higher charges than those in NaCl , Na+ & Cl- )
Ionic Radii
Positive ions are smaller compared to their atoms because it has one less shell of electrons and the
ratio of protons to electrons has increased so there is greater net force on remaining electrons
holding them more closely.
The negative ions formed from groups five to seven are larger than the corresponding atoms.
The negative ion has more electrons than the corresponding atom but the same number of protons. So the pull
of the nucleus is shared over more electrons and the attraction per electron is less, making the ion bigger.
N3- O2- F- and Na+ Mg2+ Al3+ all have the same
Ionic
Radius electronic structure (of the noble gas Ne)
There are increasing numbers of protons from N to F

and then Na to Al but the same number of electrons.
The effective nuclear attraction per electron therefore
increases and ions get smaller
N3- O2- F- (Ne) Na+ Mg2+ Al3+
Within a group the size of the Ionic radii increases going down the group. This is because
as one goes down the group the ions have more shells of electrons.
Ionic Bonding
Evidence for the existence of ions
X-ray diffraction: Electron density map of NaCl

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

•high melting points ( there are strong attractive forces between the ions)
•non conductor of electricity when solid (ions are held together tightly and can not move)
•conductor of electricity when in solution or molten. ( ions are free to move)
•brittle / easy to cleave apart
A little force will push the ions along and ions will be next to similar ions. There will be a force
of repulsion between like ions, pushing the layers apart
Migration of ions
-ve
+ve
-ve
+ve
Blue colour of
Cu2+ ions Yellow colour of A drop of potassium Manganate
migrate to the CrO42- ions solution, which is purple, is
negative migrate to the placed on moist filter paper on a
electrode positive microscope slide and the ends
electrode of the slide are connected to a
24 V DC power supply. After ten
minutes the purple colour of the
MnO4- ion has migrated to the
positive electrode
CuCrO4
Covalent Bonding
A covalent bond strong and is caused by the electrostatic attraction

between the bonding shared pair of electrons and the two nuclei.
The strength of covalent bond can be demonstrated by the high melting points of giant atomic
structures like diamond and graphite. They have high melting points because they contain many
strong covalent bonds in a macromolecular structure. It takes a lot of energy to break the many
strong bonds.
The X-ray diffractions for the hydrogen

molecule show high concentration of negative
charge between H nuclei. This negative charge
is strongly attracted by both nuclei so attractive
interactions exceed repulsive ones
In a covalent compound there is significant electron

density between the atoms
Electron Configuration Diagrams
O O
N Cl Cl
H B
H
H x N x
x xx N Cl
N N
Effect of multiple bonds on bond strength and length.

Nuclei joined by multiple (i.e. double and triple) bonds have a greater electron density between them.
This causes an greater force of attraction between the nuclei and the electrons between them, resulting in a
shorter bond length and greater bond strength.
Dative Covalent bonding .. +
A Dative covalent bond forms when the O
shared pair of electrons in the covalent bond
H H
come from only one of the bonding atoms. A
dative covalent bond is also called co-ordinate H
bonding.
Cl H
Common examples you should be able to
draw that contain dative covalent bond (e.g.
NH4+, H3O+, NH3BF3)
Cl B N H
The ammonium ion NH4+

Cl H
The direction of the arrow

goes from the atom that is
providing the lone pair to the
atom that is deficient
+
H Two aluminium chloride
+ Cl (AlCl3) molecules join
N
x together through two dative
bonds to form the dimer
H
Cl Al x Cl Al2Cl6
H
x Cl
H x Cl
x
Cl Al Cl Cl
Al
Al
Cl
The dative covalent bond acts like
an ordinary covalent bond when
x Cl Cl
thinking about shape so in NH4+ Cl
the shape is tetrahedral
Shape of molecules
Name No No lone Diagram Bond angle Examples

bonding pairs
pairs
linear 2 0 Cl Be Cl 180 CO2, CS2, HCN,
BeF2
Trigonal 3 0 Cl Cl 120 BF3, AlCl3, SO3,
planar NO3-, CO32-
B
Cl
Tetrahedral 4 0 H 109.5 SiCl4, SO42-, ClO4-,
NH4+
H H
Trigonal 3 1 .. 107 NCl3 ,PF3 ,ClO3

pyramidal ,H3O+
N
H
H
Bent 2 2 .. .. 104.5 OCl2, H2S, OF2 ,

O SCl2
H H
Trigonal 5 0 F 120 and 90 PCl5

Bipyramidal F
P F
F
F
F
Octahedral 6 0 90 SF6
F F
F F
How to explain shape 1. State number of bonding pairs and lone pairs of electrons.
2. State that electron pairs repel and try to get as far apart as possible (or to a
position of minimum repulsion.)
3. If there are no lone pairs state that the electron pairs repel equally
4. If there are lone pairs of electrons, then state that lone pairs repel more than
bonding pairs.
5. State actual shape and bond angle.
Remember lone pairs repel more than bonding pairs and so reduce bond angles (by about 2.5o
per lone pair in above examples)
Occasionally more complex shapes are seen that are variations of octahedral and trigonal
bipyramidal where some of the bonds are replaced with lone pairs. You do not need to learn the
names of these but ought to be able to work out these shapes using the method below
: : X:
:
X X : X : : X
:
:
Square planar Bond angle ~89O Bond angle ~89O Bond angles ~119 + 89O
Bond angle 180O
Bond angle 90O (Reduced by lone pair) (Reduced by lone pairs) (Reduced by lone pair)
e.g XeF4 e.g. BrF5 e.g I3- e .g.ClF3 e.g. SF4 & IF4+
Xe has 8 electrons in its outer Cl has 7 electrons in its outer I has 7 electrons in its outer
shell. 4 F’s add 4 more shell. 3 F’s add 3 more shell. 4 F’s add 4 more
electrons. This makes a total of electrons. This makes a total of electrons. Remove one electron
12 electrons made up of 4 10 electrons made up of 3 bond as positively charged. This
bond pairs and 2 lone pairs. pairs and 2 lone pairs. The makes a total of 10 electrons
The means it is a variation of means it is a variation of the 5 made up of 4 bond pairs and 1
the 6 bond pair shape bond pair shape (trigonal lone pair. The means it is a
(octahedral) bipyramidal) variation of the 5 bond pair
shape (trigonal bipyramidal)
Electronegativity and intermediate bonding
Definition F, O, N and Cl are the

most electronegative
Electronegativity is the relative tendency of an atom in a covalent bond atoms
in a molecule to attract electrons in a covalent bond to itself.
The most electronegative
Electronegativity is measured on the Pauling scale (ranges from 0 to 4) element is fluorine and it
is given a value of 4.0
Factors affecting electronegativity
Electronegativity increases across a period as the number of protons increases and the atomic radius
decreases because the electrons in the same shell are pulled in more.
It decreases down a group because the distance between the nucleus and the outer electrons increases and
the shielding of inner shell electrons increases
Intermediate bonding
Ionic and covalent bonding are the extremes of a continuum of bonding type. Differences in
electronegativity between elements can determine where a compound lies on this scale
A compound containing elements of similar electronegativity and hence a small

electronegativity difference will be purely covalent
A compound containing elements of very different electronegativity and hence a

very large electronegativity difference (> 1.7) will be ionic
Formation of a permanent dipole – (polar covalent) bond The element with the
larger
A polar covalent bond forms when the elements in the bond have different electronegativity in a
electronegativities . (Of around 0.3 to 1.7) polar compound will
be the δ- end
When a bond is a polar covalent bond it has an unequal distribution of d+ d–
electrons in the bond and produces a charge separation, (dipole) δ+ δ- H – Cl
ends.
Polar and Non Polar molecules

Symmetric molecules
A symmetric molecule (all bonds identical and no lone

pairs) will not be polar even if individual bonds within
the molecular ARE polar.
CO2 is a symmetrical molecule and
The individual dipoles on the bonds ‘cancel out’
is a non-polar molecule
due to the symmetrical shape of the molecule.
There is no NET dipole moment: the molecule is
NON POLAR
e.g. CCl4 will be non-polar whereas CH3Cl will be polar H

δ+
C δ-
H Cl
H
Experiment effect of charged rod on polar/non-polar liquids
In this experiment, a charged rod (formed by rubbing a

plastic rod) is brought close to a jet of liquid flowing from a
burette.
If the liquid is polar, the jet of liquid will be attracted to the

electrostatic force of the rod. The dipoles in the polar molecules will
all align and the negative end δ- will be attracted to the positive rod ++++++++ +
(or vice versa). The stronger the dipole the more the deflection of the
jet.
Non-polar liquids will not be deflected and attracted to the charged rod
Intermolecular Forces
London Forces London forces occur between all molecular substances and noble gases. They do
not occur in ionic substances.
London Forces are also called instantaneous, induced dipole-

dipole interactions. They occur between all simple covalent
molecules and the separate atoms in noble gases.
In any molecule the electrons are moving constantly and randomly. As
this happens the electron density can fluctuate and parts of the
molecule become more or less negative i.e. small temporary or
transient dipoles form.
These temporary dipoles can cause dipoles to form in neighbouring
molecules. These are called induced dipoles. The induced dipole is
always the opposite sign to the original one.
Main factor affecting size of London Forces

The more electrons there are in the molecule the higher the chance that temporary dipoles will form. This
makes the London forces stronger between the molecules and more energy is needed to break them so
boiling points will be greater.
The increasing boiling points of the halogens down the group 7 series can be explained by the
increasing number of electrons in the bigger molecules causing an increase in the size of the London
forces between the molecules. This is why I2 is a solid whereas Cl2 is a gas.
The increasing boiling points of the alkane homologous series can be explained by the increasing
number of electrons in the bigger molecules causing an increase in the size of the London forces
between molecules.
The shape of the molecule can also have an effect on the size of the London forces. Long straight chain
alkanes have a larger surface area of contact between molecules for London forces to form than
compared to spherical shaped branched alkanes and so have stronger London forces .
Permanent dipole-dipole forces
•Permanent dipole-dipole forces occurs between polar molecules

•It is stronger than van der waals and so the compounds have higher boiling points
•Polar molecules have a permanent dipole. (commonly compounds with C-Cl, C-F, C-Br H-Cl, C=O bonds)
•Polar molecules are asymmetrical and have a bond where there is a significant difference in
electronegativity between the atoms.
Permanent dipole forces

occur in addition to London
forces
Hydrogen bonding
It occurs in compounds that have a hydrogen atom attached to one of the three most
electronegative atoms of nitrogen, oxygen and fluorine, which must have an available lone pair of
electrons. e.g. a –O-H -N-H F- H bond. There is a large electronegativity difference between the
H and the O,N,F
+ δ-
δ- Hδ δ+
180o N O
180 o H
δ+ δ- δ - δ +
δ+
H H δ+ H
H F H F
δ +
δ+
δ- H δ+
N H
Always show the lone pair of electrons on the δ-
O,F,N and the dipoles and all the δ- δ+ charges H
δ +
O
Hδ +
H δ+ δ+
Hydrogen bonding occurs in addition to London forces δ+ H H
The hydrogen bond should have an bond angle of 180o with one O
of the bonds in one of the molecules
δ-
The bond angle is 180O around the H atom because there are Water can form two hydrogen bonds
two pairs of electrons around the H atom involved in the per molecule, because the
hydrogen bond. These pairs of electrons repel to a position of electronegative oxygen atom has two
minimum repulsion, as far apart as possible. lone pairs of electrons on it.
It can therefore form stronger
Alcohols, carboxylic acids, proteins, amides all can form hydrogen bonds hydrogen bonding and needs more
energy to break the bonds, leading to
a higher boiling point.
Alcohols form hydrogen bonds. This means alcohols have

higher boiling points and relatively low volatility compared to Ice H H
alkanes with a similar number of electrons O
H
H
O O
H
H H
HO O
H H
In ice the molecules are held further
apart by the hydrogen bonds than in
liquid water and this explains the lower
density of ice
Hydrogen bonding is stronger than the other two
types of intermolecular bonding.
400
H2O
The anomalously high boiling points of H2O,
NH3 and HF are caused by the hydrogen bonding
Boiling point K
300 HF H2Te
between these molecules in addition to their
London forces. The additional forces require more H2Se SbH3
NH3 H2S
energy to break and so have higher boiling points HI
AsH3
200 HBr
PH3 HCl SnH4
GeH4
The general increase in boiling point from H2S to SiH4
H2Te or from HCl to HI is caused by increasing 100 CH4
London forces between molecules due to an
increasing number of electrons.
25 50 75 100 125
Molecular mass
Solvents and Solubility
Solubility of a solute in a solvent is a complicated balance of energy required to break bonds in the solute
and solvent against energy given out making new bonds between the solute and solvent.
Ionic substances dissolving in water

hydration of the ions
When an ionic lattice dissolves in water it

involves breaking up the bonds in the lattice
and forming new bonds between the metal
ions and water molecules.
The negative ions are attracted to the δ+

hydrogens on the polar water molecules and
The higher the charge density the greater the hydration
the positive ions are attracted to the δ- oxygen
enthalpy (e.g. smaller ions or ions with larger charges)
on the polar water molecules.
as the ions attract the water molecules more strongly.
Solubility of simple alcohols

δ- δ+ δ- +
O H O H δ
H
The smaller alcohols are soluble in water
because they can form hydrogen bonds C H
H δ+
with water. The longer the hydrocarbon H
chain the less soluble the alcohol. C
H
H
Insolubility of compounds in water
Compounds that cannot form hydrogen bonds with water molecules, e.g. polar molecules such as
halogenoalkanes or non polar substances like hexane will be insoluble in water.
Solubility in non-aqueous solvents
Compounds which have similar intermolecular

forces to those in the solvent will generally dissolve
Non-polar solutes will dissolve in non-polar solvents. e.g. Iodine which has only London forces between
its molecules will dissolve in a non polar solvent such as hexane which also only has London forces.
Propanone is a useful solvent because it has both polar and

CH3
non polar characteristics. It can form London forces with some
non polar substances such as octane with its CH3 groups. Its δ- δ+ δ- δ+
polar C=O bond can also hydrogen bond with water. O H O C
δ +
H CH3
Metallic bonding
Metals consist of giant lattices of metal ions in a sea of delocalised electrons
Definition: A metallic bond is the electrostatic force of attraction between the

positive metal ions and the delocalised electrons
sodium
The three main factors that affect the strength of a metallic bond are:
1. Number of protons/ Strength of nuclear attraction.
The more protons the stronger the bond
2. Number of delocalised electrons per atom (the outer shell electrons are delocalised)
The more delocalised electrons the stronger the bond
3. Size of ion.
The smaller the ion, the stronger the bond.
Metals have high melting points because the strong electrostatic forces between positive ions
and sea of delocalised electrons require a lot of energy to break
Example
Mg has stronger metallic bonding than Na and hence a higher
melting point. The Metallic bonding gets stronger because in Mg
there are more electrons in the outer shell that are released to the
sea of electrons. The Mg ion is also smaller and has one more
proton. There is therefore a stronger electrostatic attraction
between the positive metal ions and the delocalised electrons
and higher energy is needed to break bonds.
magnesium
Metals can conduct electricity well because the delocalised electrons can move through the structure
Metals are malleable because the positive ions in the lattice are all identical. So the planes of ions
can slide easily over one another. The attractive forces in the lattice are the same whichever ions are
adjacent
2B Structure: ionic, metallic, molecular and giant covalent (macromolecular).
You should be able to draw the following diagrams or describe the structure in words to
show the four different types of crystal. You should also be able to explain the properties of
these solids.
Giant lattices are present in:
i ionic solids (giant ionic lattices)
ii covalently bonded solids, such as diamond, graphite and silicon(IV) oxide (giant covalent lattices)
iii solid metals (giant metallic lattices)
Ionic: sodium chloride
Giant Ionic lattice showing alternate

Na+ and Cl- ions
Giant Covalent: diamond Giant Covalent: Graphite
Planar arrangement of carbon

Tetrahedral arrangement of atoms in layers. 3 covalent bonds
per atom in each layer. 4th outer
carbon atoms. 4 covalent
electron per atom is delocalised.
bonds per atom Delocalised electrons between
layers.
Both these macromolecular structures have very high melting points because of strong covalent
forces in the giant structure. It takes a lot of energy to break the many strong covalent bonds
Metallic: magnesium or sodium
Use this
diagram Giant metallic lattice showing close
for any packing magnesium ions
metal
Molecular: Ice This is a difficult diagram

to draw.
Molecular: Iodine H H The main point to show is
O a central water molecule
with two ordinary covalent
bonds and two hydrogen
Regular arrangement of I2 H bonds in a tetrahedral
molecules held together by H arrangement
O O
weak London forces H
H H The molecules are held
HO O further apart than in liquid
H H water and this explains the
lower density of ice
Carbon Allotropes
Macromolecular: Graphite
Macromolecular: diamond
Planar arrangement of carbon
atoms in layers. 3 covalent
Tetrahedral arrangement of
bonds per atom in each layer.
carbon atoms. 4 covalent
4th outer electron per atom is
bonds per atom
delocalised. Delocalised
electrons between layers.
Diamond cannot conduct electricity because all 4 Graphite can conduct electricity well between
electrons per carbon atoms are involved in layers because one electron per carbon is free and
covalent bonds. They are localised and cannot delocalised, so electrons can move easily along
move layers.
It does not conduct electricity between layers
because the energy gap between layers is too
large for easy electron transfer.
Both these macromolecular structures have very high melting points because of strong covalent
forces in the giant structure. It takes a lot of energy to break the many strong covalent bonds
Graphene
Graphene is a new substance that is a one layer of graphite.i.e. 3 covalent bonds per atom and
the 4th outer electron per atom is delocalised.
These have very high tensile strength because of the strong structure of many strong covalent
bonds
Graphene can conduct electricity well along the structure because one electron per carbon is free
and delocalised, so electrons can move easily along the structure.
Carbon nanotubes
These have very high tensile strength because of the strong

structure of many strong covalent bonds
Nanotubes can conduct electricity well along the tube

because one electron per carbon is free and delocalised,
so electrons can move easily along the tube.
Nanotubes have potentially many uses. One being the

potential to us as vehicles to deliver drugs to cells.
There are delocalized electrons in buckminsterfullerene.
Bonding and Structure
Bonding Structure Examples
Ionic : electrostatic force of Sodium chloride

attraction between Magnesium oxide
oppositely charged ions Giant Ionic Lattice
Covalent : shared pair of Simple molecular: Iodine

electrons With intermolecular forces (London Ice
forces, permanent dipoles, hydrogen Carbon dioxide
bonds) between molecules Water
Methane
Covalent : shared pair of Macromolecular: Diamond

electrons giant molecular structures. Graphite
Silicon dioxide
Silicon
Metallic: electrostatic Giant metallic Magnesium, Sodium

force of attraction between lattice (all metals)
the metal positive ions and
the delocalised electrons
Only use the words molecules and intermolecular forces when talking about simple molecular substances
Property Ionic Molecular (simple) Macromolecular Metallic
boiling and high- because low- because of high- because of high- strong electrostatic forces
melting of giant lattice weak intermolecular many strong covalent between positive ions and sea of
points of ions with forces between bonds in delocalised electrons
strong molecules (specify macromolecular
electrostatic type e.g London structure. Take a lot
forces forces/hydrogen of energy to break the
between bond) many strong bonds
oppositely
charged ions.
Solubility in Generally generally poor insoluble insoluble

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

when molten move
general crystalline mostly gases and solids shiny metal

description solids liquids Malleable as the positive ions in
the lattice are all identical. So the
planes of ions can slide easily
over one another
-attractive forces in the lattice are
the same whichever ions are
adjacent
2. Redox
oxidation is the process of electron loss: reduction is the process of electron gain:
Zn Zn2+ + 2e- Cl2 + 2e- 2Cl-
It involves an increase in oxidation number It involves a decrease in oxidation number
Rules for assigning oxidation numbers

eg . Zn, Cl2, O2, Ar all have oxidation numbers of zero
1. All uncombined elements have an oxidation number of zero
2. The oxidation numbers of the elements in a compound add In NaCl Na= +1 Cl= -1
up to zero Sum = +1 -1 = 0
3. The oxidation number of a monoatomic ion is equal to the

e.g. Zn2+ = +2 Cl- = -1
ionic charge
4. In a polyatomic ion (CO32-) the sum of the individual e.g. in CO32- C = +4 and O = -2
oxidation numbers of the elements adds up to the charge
sum = +4 + (3 x -2) = -2
on the ion
5. Several elements have invariable oxidation numbers in their
common compounds.
Group 1 metals = +1
Group 2 metals = +2
Al = +3 We use these rules to
H = +1 (except in metal hydrides where it is –1 eg NaH) identify the oxidation
numbers of elements that
F = -1 have variable oxidation
Cl, Br, I = –1 except in compounds with oxygen and fluorine numbers.
O = -2 except in peroxides (H2O2 ) where it is –1 and in compounds with fluorine.
Note the oxidation number of Cl

What is the oxidation number of Fe in FeCl3
in CaCl2 = -1 and not -2 because
Using rule 5, Cl has an O.N. of –1 there are two Cl’s
Using rule 2, the O.N. of the elements must add up to 0 Always work out the oxidation for
one atom of the element
Fe must have an O.N. of +3
in order to cancel out 3 x –1 = -3 of the Cl’s
Naming using oxidation number
If an element can have various oxidation numbers then the oxidation number of that element in a
compound can be given by writing the number in roman numerals
FeCl2: Iron (II) chloride

FeCl3 Iron (III) chloride
MnO2 Manganese (IV) Oxide
In IUPAC convention the various forms of sulfur,nitrogen and chlorine compounds where oxygen
is combined are all called sulfates, nitrates and chlorates with relevant oxidation number given in
roman numerals. If asked to name these compounds remember to add the oxidation number.
NaClO: sodium chlorate(I) NaNO3 sodium nitrate (V)

NaClO3: sodium chlorate(V) NaNO2 sodium nitrate (III)
K2SO4 potassium sulfate(VI)
K2SO3 potassium sulfate(IV)
Redox equations and half equations
Br2 (aq) + 2I- (aq) I2 (aq) + 2 Br- (aq)
Br2 (aq) + 2e- + 2 Br- (aq) 2I- (aq) I2 (aq) + 2 e-

Br has reduced as it has gained electrons I has oxidised as it has lost electrons
A reduction half equation only shows the parts An oxidation half equation only shows the reducing agents are
of a chemical equation involved in reduction parts of a chemical equation involved in electron donors
The electrons are on the left oxidation
The electrons are on the right
oxidising agents are
electron acceptors
The oxidising agent is Bromine The reducing agent is the Iodide
water . It is an electron acceptor ion. It is an electron donor
When naming oxidising
and reducing agents
An oxidising agent (or oxidant) is the A reducing agent (or reductant) is the
species that causes another element to species that causes another element always refer to full name
oxidise. It is itself reduced in the reaction reduce. It is itself oxidised in the reaction. of substance and not
just name of element
Redox Reactions
metals generally form ions by losing non-metals generally react by gaining

electrons with an increase in oxidation electrons with a decrease in oxidation
number to form positive ions: number to form negative ions
Zn Zn2+ + 2e- Cl2 + 2e- 2Cl-
Oxygen is reducing because Tungsten is reducing because

its oxidation number is its oxidation number is
decreasing from 0 to -2 decreasing from +6 to 0
0 -2 +6 0
4Li + O2 2Li2O WO3 + 3H2 W + 3H2O
0 +1 0 +1
Lithium is oxidising because its Hydrogen is oxidising

oxidation number is increasing from 0 because its oxidation number
to +1 is increasing from 0 to +1
Nitrogen is reducing because Chlorine is reducing because

its oxidation number is its oxidation number is
decreasing from +5 to+4 decreasing from +1 to -1
+5 +4 +1 -1
2Sr(NO3)2 2SrO + 4NO2 + O2 2 NH3 + NaClO N2H4 + NaCl + H2O
-2 0 -3 -2
Oxygen is oxidising because its oxidation Nitrogen is oxidising because its oxidation
number is increasing from -2 to 0 number is increasing from -3 to -2
Note that not all the oxygen atoms are

changing oxidation number in this reaction
Redox Reactions of Metals and acid
ACID + METAL SALT + HYDROGEN
Hydrogen is reducing Be able to write equations for reactions of

because its oxidation number metals with hydrochloric acid and sulphuric
is decreasing from +1 to 0 acid
+1 0 Fe + H2SO4 FeSO4 +H2

2HCl + Mg MgCl2 +H2
0 +2
Observations: These reaction will
Magnesium is oxidising effervesce because H2 gas is evolved
because its oxidation number is and the metal will dissolve
increasing from 0 to +2
Disproportionation
Disproportionation is the name for a reaction where

an element in a single species simultaneously
oxidises and reduces.
Chlorine is both simultaneously reducing and
Cl2(aq) + H2O(l) HClO(aq) + HCl (aq) oxidising changing its oxidation number from 0 to
-1 and 0 to +1
Copper(I) ions (+1) when reacting with sulphuric acid will

2Cu+ Cu + Cu2+
disproportionate to Cu2+ (+2) and Cu (0) metal
Balancing Redox equations
Writing half equations
1. Work out oxidation numbers for element being oxidised/ reduced Zn Zn2+ Zn changes from 0 to +2
2. Add electrons equal to the change in oxidation number

For reduction add e’s to reactants
Zn Zn2+ + 2e-
For oxidation add e’s to products
3. check to see that the sum of the charges on the reactant side
equals the sum of the charges on the product side 0 +2 –2 =0
More complex Half equations

If the substance that is being oxidised or reduced contains a varying amount of O (eg In acidic conditions
MnO4- Mn2+ ) then the half equations are balanced by adding H+, OH- ions and H2O. use H+ and H2O
Example: Write the half equation for the change MnO4- Mn2+
Mn changes from +7 to +2
1. Balance the change in O.N. with electrons Add 5 electrons to reactants MnO4- + 5e- Mn2+
2. Add H2O in products to balance O’s in MnO4- MnO4- + 5e- Mn2+ + 4H2O
3. Add H+ in reactants to balance H’s in H2O MnO4- + 8H+ + 5e- Mn2+ + 4H2O
equals the sum of the charges on the product side -1 + 8 -5 = +2 +2
Example: Write the half equation for the change SO42- SO2
S changes from +6 to +4
1. Balance the change in O.N. with electrons Add 2 electrons to reactants SO42- + 2e- SO2
2. Add H2O in products to balance O’s in SO42- SO42- + 2e- SO2 + 2H2O
3. Add H+ in reactants to balance H’s in H2O SO42- + 4H+ + 2e- SO2 + 2H2O
equals the sum of the charges on the product side -4 + 4 = 0 0
Combining half equations

To combine two half equations there must be
To make a full redox equation combine a reduction
equal numbers of electrons in the two half
half equation with a oxidation half equation
equations so that the electrons cancel out
Example 1
Reduction MnO4- + 8 H+ + 5 e- → Mn2+ + 4 H2O x2

Multiply the half equations to get
Oxidation C2O42- → 2 CO2 + 2 e- x5 equal electrons
2MnO4- + 16 H+ + 5C2O42- → 2Mn2+ + 10 CO2 + 8 H2O Add half equations together and cancel
electrons
Example 2
Reduction SO42- + 10H+ + 8e- H2S+ 4H2O Multiply the half equations to get
equal electrons
Oxidation 2I- → I2 + 2 e- x4
Add half equations together and
8I- + SO42- + 10H+ H2S+ 4I2 + 4H2O cancel electrons
4. Inorganic Chemistry and the Periodic Table
4A: Group 2
Melting points
Down the group the melting points decrease. The
Atomic radius
metallic bonding weakens as the atomic size
Atomic radius increases down the Group.
increases. The distance between the positive ions and
As one goes down the group, the atoms have more
delocalized electrons increases. Therefore the
shells of electrons making the atom bigger.
electrostatic attractive forces between the positive
ions and the delocalized electrons weaken.

The outermost electrons are held more weakly because they are successively further from the nucleus
in additional shells.
In addition, the outer shell electrons become more shielded from the attraction of the nucleus by the
repulsive force of inner shell electrons
Group 2 reactions Reactivity of group 2 metals increases down the group
The reactivity increases down the group as the atomic radii increase there is more shielding. The nuclear
attraction decreases and it is easier to remove (outer) electrons and so cations form more easily
Reactions with oxygen.
Mg will also react slowly with oxygen without a flame.
The group 2 metals will burn in oxygen. Mg ribbon will often have a thin layer of magnesium oxide on it
Mg burns with a bright white flame. formed by reaction with oxygen.
2Mg + O2 2MgO 2Mg + O2 2MgO
This needs to be cleaned off by emery paper before doing
MgO is a white solid with a high melting reactions with Mg ribbon.
point due to its ionic bonding. If testing for reaction rates with Mg and acid, an un-cleaned Mg
ribbon would give a false result because both the Mg and MgO
would react but at different rates.
Mg + 2HCl MgCl2 + H2
MgO + 2HCl MgCl2 + H2O
Reactions with chlorine
The group 2 metals will react with chlorine

Mg + Cl2 MgCl2
Reactions with water.
Magnesium burns in steam to produce Mg will also react with warm water, giving a different
magnesium oxide and hydrogen. The Mg magnesium hydroxide product.
would burn with a bright white flame.
Mg + 2 H2O Mg(OH)2 + H2
Mg (s) + H2O (g) MgO (s) + H2 (g)
This is a much slower reaction than the reaction with
steam and there is no flame.
The hydroxides produced make the water alkaline

The other group 2 metals will react with cold water with
increasing vigour down the group to form hydroxides.
One would observe:
Ca + 2 H2O (l) Ca(OH)2 (aq) + H2 (g)
•fizzing, (more vigorous down group)
Sr + 2 H2O (l) Sr(OH)2 (aq) + H2 (g)
•the metal dissolving, (faster down group)
Ba + 2 H2O (l) Ba(OH)2 (aq) + H2 (g)
•the solution heating up (more down group)
•and with calcium a white precipitate
appearing (less precipitate forms down
group)
Reactions of the Oxides of Group 2 elements with water
Group 2 ionic oxides react with water to form hydroxides
The ionic oxides are basic as the oxide ions accept protons to become hydroxide ions in this
reaction (acting as a bronsted lowry base)
MgO (s) + H2O (l) Mg(OH)2 (s) pH 9
Mg(OH)2 is only slightly soluble in water so fewer free OH- ions are produced and so lower pH
CaO (s) + H2O (l) Ca(OH)2 (aq) pH 12
Reactions of the Oxides of Group 2 elements with Acids

MgO (s) + 2 HCl (aq) MgCl2 (aq) + H2O (l)
SrO (s) + 2 HCl (aq) SrCl2 (aq) + H2O (l)

CaO (s) + H2SO4 (aq) CaSO4 (aq) + H2O (l)
Reactions of the hydroxides of Group 2 elements with Acids

2HNO3 (aq) + Mg(OH)2 (aq) Mg(NO3)2 (aq) + 2H2O (l)
2HCl (aq) + Mg(OH)2 (aq) MgCl2 (aq) + 2H2O (l)
Solubility of hydroxides
Group II hydroxides become more soluble down the group.
All Group II hydroxides when not soluble appear as white precipitates.
Magnesium hydroxide is classed as insoluble in water. Calcium hydroxide is reasonably soluble

in water. It is used in agriculture to
Simplest Ionic Equation for formation of Mg(OH)2 (s)
neutralise acidic soils.
Mg2+ (aq) + 2OH-(aq) Mg(OH)2 (s).
An aqueous solution of calcium hydroxide
A suspension of magnesium hydroxide in water will appear is called lime water and can be used a test
slightly alkaline (pH 9) so some hydroxide ions must therefore for carbon dioxide. The limewater turns
have been produced by a very slight dissolving. cloudy as white calcium carbonate is
produced.
Magnesium hydroxide is used in medicine (in suspension as
milk of magnesia) to neutralise excess acid in the stomach and Ca(OH)2 (aq) + CO2 (g) CaCO3 (s) + H2O(l)
to treat constipation.
Mg(OH)2 + 2HCl MgCl2 + 2H2O Barium hydroxide would easily dissolve
in water. The hydroxide ions present
It is safe to use because it so weakly alkaline. It is preferable to would make the solution strongly
using calcium carbonate as it will not produce carbon dioxide alkaline.
gas.
Ba(OH)2 (S) + aq Ba2+ (aq) + 2OH-
(aq)
Solubility of Sulphates
Group II sulphates become less soluble down the group.
BaSO4 is the least soluble.
If Barium metal is reacted with sulphuric acid it will only react slowly as the insoluble Barium sulphate
produced will cover the surface of the metal and act as a barrier to further attack.
Ba + H2SO4 BaSO4 + H2
The same effect will happen to a lesser extent with metals going up the group as the solubility increases.
The same effect does not happen with other acids like hydrochloric or nitric as they form soluble group 2
salts.
Thermal decomposition of Group 2 carbonates
Thermal decomposition is defined as the use
Group 2 carbonates decompose on heating to produce
of heat to break down a reactant into more than
group 2 oxides and carbon dioxide gas.
one product
MgCO3(s) MgO(s) + CO2(g)
CaCO3(s) CaO(s) + CO2(g) The ease of thermal decomposition
decreases down the group
Group 2 carbonates are more thermally stable as you go down
the group. As the cations get bigger they have less of a
polarising effect and distort the carbonate ion less. The C-O
bond is weakened less so it less easily breaks down
Group 1 carbonates do not decompose with the exception of Lithium.

As they only have +1 charges they don’t have a big enough charge
density to polarise the carbonate ion. Lithium is the exception
because its ion is small enough to have a polarising effect
Li2CO3(s) Li2O(s) + CO2(g)
There are a number of experiments that can be done to investigate the

ease of decomposition.
One is to heat a known mass of carbonate in a side arm boiling tube lime water
and pass the gas produced through lime water. Time for the first
permanent cloudiness to appear in the limewater. Repeat for different
carbonates using the same moles of carbonate/same volume of
limewater/same Bunsen flame and height of tube above flame.
Heat
Thermal decomposition of Group 2 Nitrates

Group 2 nitrates decompose on heating to produce group
2 oxides, oxygen and nitrogen dioxide gas.
2Mg(NO3)2 → 2MgO + 4NO2 + O2
You would observe brown gas evolving (NO2) and the
The ease of thermal decomposition
White nitrate solid is seen to melt to a colourless solution
decreases down the group
and then resolidify
The explanation for change in thermal stability is the same as for carbonates
Magnesium nitrate decomposes the easiest because the Mg2+ ion is smallest and has the greater charge
density. It causes more polarisation of the nitrate anion and weakens the N―O bond
Group 1 nitrate do not decompose in the same way as group 2 with

the exception of Lithium nitrate. They decompose to give a Nitrate
(III) salt and oxygen.
2NaNO3 → 2NaNO2 + O2
Lithium nitrate decomposes in the
Sodium Sodium same way as group 2 nitrates
Nitrate(V) Nitrate(III)
4 LiNO3 → 2Li2O + 4NO2 + O2
Flame tests
Method Lithium : Scarlet red
Use a nichrome wire ( nichrome is an unreactive metal Sodium : Yellow
and will not give out any flame colour) Potassium : lilac
Clean the wire by dipping in concentrated hydrochloric Rubidium : red
Caesium: blue
acid and then heating in Bunsen flame Magnesium: no flame colour (energy emitted
If the sample is not powdered then grind it up. of a wavelength outside visible spectrum)
Dip wire in solid and put in bunsen flame and observe Calcium: brick red
flame Strontium: red
Barium: apple green
Explanation for occurrence of flame
In a flame test the heat causes the electron to move to a
higher energy level.
The electron is unstable at the higher energy level and so
drops back down. As it drops back down from the
higher to a lower energy level, energy is emitted in the
form of visible light energy with the wavelength of the
observed light
4B Halogens Fluorine (F2): very pale yellow gas. It is highly reactive
Chlorine : (Cl2) greenish, reactive gas, poisonous in high concentrations
Bromine (Br2) : red liquid, that gives off dense brown/orange poisonous fumes
Iodine (I2) : shiny grey solid sublimes to purple gas.
Trend in melting point and boiling point Trend in electronegativity

Increase down the group Electronegativity is the relative tendency of an atom in a
molecule to attract electrons in a covalent bond to itself.
As the molecules become larger they have
more electrons and so have larger London As one goes down the group the electronegativity of the
forces between the molecules. As the elements decreases.
intermolecular forces get larger more energy
As one goes down the group the atomic radii increases due
has to be put into break the forces. This
to the increasing number of shells. The nucleus is therefore
increases the melting and boiling points
less able to attract the bonding pair of electrons
The reactivity of the halogens decreases down the group as the atoms get bigger with more shielding so
they less easily attract and accept electrons. They therefore form -1 ions less easily down the group
1. The oxidation reactions of halide ions by halogens.
A halogen that is a strong oxidising agent will The oxidising strength decreases down the group.
displace a halogen that has a lower oxidising Oxidising agents are electron acceptors.
power from one of its compounds
know these
Chlorine will displace both bromide and iodide ions; bromine will displace iodide ions
observations !
Chlorine (aq) Bromine (aq) Iodine (aq) The colour of the solution in
the test tube shows which free
potassium Very pale green Yellow solution, no Brown solution, halogen is present in solution.
chloride (aq) solution, no reaction no reaction Chlorine =very pale green
reaction solution (often colourless),
potassium Yellow solution, Cl Yellow solution, no Brown solution, Bromine = yellow solution
bromide (aq) has displaced Br reaction no reaction Iodine = brown solution
(sometimes black solid
potassium Brown solution, Cl Brown Solution, Br Brown Solution,
present)
iodide (aq) has displaced I has displaced I no reaction
Observations if an organic solvent is added

Chlorine (aq) Bromine (aq) Iodine (aq)
The colour of the organic
potassium colourless, no yellow, no purple, no solvent layer in the test tube
chloride (aq) reaction reaction reaction shows which free halogen is
present in solution.
potassium yellow, Cl has yellow, no purple, no Chlorine = colourless
bromide (aq) displaced Br reaction reaction Bromine = yellow
Iodine = purple
potassium purple, Cl has purple, Br has purple, no
iodide (aq) displaced I displaced I reaction
Cl2(aq) + 2Br – (aq) 2Cl – (aq) + Br2(aq)

Cl2(aq) + 2I – (aq) 2Cl – (aq) + I2(aq)
Br2(aq) + 2I – (aq) 2Br – (aq) + I2(aq)
The oxidation reactions of metals and metal ion by halogens. In all reactions where halogens
are reacting with metals, the
3Cl2(g) + 2 Fe (s) 2 FeCl3 (s) Br2(l) + 2Na (s) 2NaBr (s) metals are being oxidised
Cl2(g) + 2Fe2+ (aq) 2 Cl- (aq) + 2Fe3+ (aq)

Chlorine and Bromine can oxidise Fe2+ to Fe3+. Iodine
is not strong enough oxidising agent to do this reaction.
2I- (aq) + 2Fe3+ (aq) I2 (aq) + 2Fe2+ (aq)
The reaction is reversed for Iodine
The disproportionation reactions of chlorine and chlorate(I).
Disproportionation is the name for a reaction where Chlorine is both simultaneously reducing and
an element simultaneously oxidises and reduces. oxidising changing its oxidation number from 0 to
-1 and 0 to +1
Chlorine with water:
Cl2(aq) + H2O(l) HClO(aq) + HCl (aq)
If some universal indicator is added to the solution it will

The pale greenish colour of these solutions
first turn red due to the acidity of both reaction products. It
is due to the Cl2
will then turn colourless as the HClO bleaches the colour.
Chlorine is used in water treatment to kill bacteria. It has been used to treat drinking water and the water in
swimming pools. The benefits to health of water treatment by chlorine outweigh its toxic effects.
Reaction of halogens with cold dilute NaOH solution:

Cl2, Br2, and I2 in aqueous solutions will react with cold sodium hydroxide. The colour of the halogen solution
will fade to colourless
Cl2(aq) + 2NaOH(aq) NaCl (aq) + NaClO (aq) + H2O(l)
The mixture of NaCl and NaClO is used as Bleach and to disinfect/ kill bacteria
Reaction of halogens with hot dilute NaOH solution:
With hot alkali disproportionation also occurs but the halogen that is oxidised goes to a higher
oxidation state.
3Cl2 (aq) + 6 NaOH(aq) 5 NaCl (aq) + NaClO3 (aq) + 3H2O (l)
3I2 (aq) + 6KOH (aq) 5 KI (aq) + KIO3 (aq) + 3H2O (l)
3I2 (aq) + 6OH- (aq) 5 I- (aq) + IO3- (aq) + 3H2O (l)
In IUPAC convention the various forms of sulfur and chlorine compounds where oxygen is
combined are all called sulfates and chlorates with relevant oxidation number given in roman
numerals. If asked to name these compounds remember to add the oxidation number.
NaClO: sodium chlorate(I)

NaClO3: sodium chlorate(V)
K2SO4 potassium sulfate(VI)
K2SO3 potassium sulfate(IV)
The reaction of halide salts with concentrated sulphuric acid.
The Halides show increasing power as

Explanation of differing reducing power of halides
reducing agents as one goes down the
A reducing agent donates electrons.
group. This can be clearly demonstrated in
The reducing power of the halides increases down group 7
the various reactions of the solid halides with
They have a greater tendency to donate electrons.
concentrated sulphuric acid.
This is because as the ions get bigger it is easier for the
Know the equations and observations of outer electrons to be given away as the pull from the nucleus
these reactions very well. on them becomes smaller.
Fluoride and Chloride

The H2SO4 is not strong enough an oxidising reagent to oxidise the chloride and
fluoride ions. No redox reactions occur. Only acid-base reactions occur.
NaF(s) + H2SO4(l) NaHSO4(s) + HF(g)

These are acid –base reactions and
Observations: White steamy fumes of HF are evolved.
not redox reactions. H2SO4 plays the
NaCl(s) + H2SO4(l) NaHSO4(s) + HCl(g) role of an acid (proton donor).
Observations: White steamy fumes of HCl are evolved.
Bromide
Br- ions are stronger reducing agents than Cl- and F- and after the initial acid-
base reaction reduce the Sulphur in H2SO4 from +6 to + 4 in SO2
Observations: White steamy
Acid- base step: NaBr(s) + H SO (l) NaHSO (s) + HBr(g) fumes of HBr are evolved.
2 4 4
Redox step: 2HBr + H2SO4 Br2(g) + SO2(g) + 2H2O(l) Red fumes of Bromine are also
evolved and a colourless, acidic gas
SO2
Ox ½ equation 2Br - Br2 + 2e-
Re ½ equation H2SO4 + 2 H+ + 2 e- → SO2 + 2 H2O Reduction product = sulphur dioxide
Note the H2SO4 plays the role of acid in the first step producing HBr
and then acts as an oxidising agent in the second redox step.
Iodide
I- ions are the strongest halide reducing agents. They can reduce the Sulphur
from +6 in H2SO4 to + 4 in SO2, to 0 in S and -2 in H2S.
NaI(s) + H2SO4(l) NaHSO4(s) + HI(g) Observations:

2HI + H2SO4 I2(s) + SO2(g) + 2H2O(l) White steamy fumes of HI are evolved.
6HI + H2SO4 → 3 I2 + S (s) + 4 H2O (l) Black solid and purple fumes of Iodine are
8HI + H2SO4 4I2(s) + H2S(g) + 4H2O(l) also evolved
A colourless, acidic gas SO2
A yellow solid of Sulphur
Ox ½ equation 2I - I2 + 2e- H2S (Hydrogen Sulphide), a gas with a bad egg
Re ½ equation H2SO4 + 2 H+ + 2 e- → SO2 + 2 H2O smell,
Re ½ equation H2SO4 + 6 H+ + 6 e- → S + 4 H2O
Reduction products = sulphur dioxide,
Re ½ equation H2SO4 + 8 H+ + 8 e- → H2S + 4 H2O sulphur and hydrogen sulphide
Note the H2SO4 plays the role of acid in the first step producing HI and
then acts as an oxidising agent in the three redox steps
Often in exam questions these redox reactions are

worked out after first making the half-equations
The reactions of halide ions with silver nitrate. The role of nitric acid is to react with any carbonates
present to prevent formation of the precipitate
This reaction is used as a test to identify which halide ion Ag2CO3. This would mask the desired observations
is present. The test solution is made acidic with nitric
2 HNO3 + Na2CO3 2 NaNO3 + H2O + CO2
acid, and then Silver nitrate solution is added dropwise.
Fluorides produce no precipitate

Chlorides produce a white precipitate Effect Of Light on Silver Halides
Ag+(aq) + Cl- (aq) AgCl(s)
The precipitates ( except AgI) darken in sunlight forming
Bromides produce a cream precipitate
silver. This reaction is used in photography to form the
Ag+(aq) + Br- (aq) AgBr(s)
dark bits on photographic film
Iodides produce a pale yellow precipitate
Ag+(aq) + I- (aq) AgI(s)
Silver chloride dissolves in dilute ammonia to form a
Effect Of ammonia on Silver Halides complex ion
AgCl(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Cl- (aq)
Colourless solution
The silver halide precipitates can be
Silver bromide dissolves in concentrated ammonia to form a
treated with ammonia solution to help
complex ion
differentiate between them if the
AgBr(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Br - (aq)
colours look similar:
Colourless solution
Silver iodide does not react with ammonia – it is too insoluble.
Producing hydrogen halides
Hydrogen halides are made by the reaction of solid

sodium halide salts with phosphoric acid
This is the apparatus
used to make the
NaCl(s) + H3PO4(l) NaH2PO4(s) + HCl(g)
hydrogen halide using
phosphoric acid.
Observations: White steamy fumes of the Hydrogen
Notice the downward
Halides are evolved.
delivery which is used
The Steamy fumes of HCl are produced when the HCl because the hydrogen
meets the air because it dissolves in the moisture in the halides are more dense
air than air
Phosphoric acid is not an oxidising agent and so does not oxidise HBr and HI. Phosphoric acid is more
suitable for producing hydrogen halides than the ones with concentrated sulphuric acid to make HCl, HBr,
and HI because there are no extra redox reactions taking place and no other products
Solubility in water : Hydrogen Halide All the hydrogen halides react readily with
The hydrogen halides ammonia to give the white smoke of the
are all soluble in ammonium halide
The water quickly
water. They dissolve rises up the tube
to form acidic HCl(g) + NH3 (g) NH4Cl (s)
solutions. HBr(g) + NH3 (g) NH4Br (s)
HI(g) + NH3 (g) NH4I (s)
This can be used as a test for the

presence of hydrogen halides
4C Analysis of Inorganic Compounds
Testing for Negative ions (anions)
Testing for Presence of a carbonate CO32- and hydrogencarbonates HCO3-
Add any dilute acid and observe effervescence.
Bubble gas through limewater to test for CO2 – will turn limewater cloudy Fizzing due to CO2 would be
observed if a carbonate or a
2HCl + Na2CO3 2NaCl + H2O + CO2 2H+ + CO32- H2O + CO2 hydrogencarbonate was present
HCl + NaHCO3 NaCl + H2O + CO2 H+ + HCO3- H2O + CO2
Testing for Presence of a sulfate Ba2+ (aq) + SO42-(aq) BaSO4 (s).

Acidified BaCl2 solution is used as a reagent to test for sulfate ions
Other anions should give a negative
If Barium Chloride is added to a solution that contains sulfate ions a
result which is no precipitate forming
white precipitate forms
The acid is needed to react with carbonate impurities that Sulfuric acid cannot be used to acidify the
are often found in salts which would form a white Barium mixture because it contains sulfate ions
carbonate precipitate and so give a false result which would form a precipitate
Testing for halide ions with silver nitrate. The role of nitric acid is to react with any carbonates
This reaction is used as a test to identify which halide ion present to prevent formation of the precipitate
is present. The test solution is made acidic with nitric Ag2CO3. This would mask the desired observations
acid, and then Silver nitrate solution is added dropwise. 2 HNO3 + Na2CO3 2 NaNO3 + H2O + CO2
Fluorides produce no precipitate Hydrochloric acid cannot be used to

Chlorides produce a white precipitate acidify the mixture because it contains
Ag+(aq) + Cl- (aq) AgCl(s) chloride ions which would form a
Bromides produce a cream precipitate precipitate
Ag+(aq) + Br- (aq) AgBr(s)
Iodides produce a pale yellow precipitate
Ag+(aq) + I- (aq) AgI(s)
The silver halide precipitates can be treated with ammonia solution to help
differentiate between them if the colours look similar:
Silver chloride dissolves in dilute ammonia to form a complex ion

AgCl(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Cl- (aq)
Colourless solution
Silver bromide dissolves in concentrated ammonia to form a complex ion
AgBr(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Br - (aq)
Colourless solution
Silver iodide does not react with ammonia – it is too insoluble.
Testing for positive ions (cations)

Ammonia gas can be identified by
Test for ammonium ion NH4+, by reaction with warm its pungent smell or by turning red
NaOH(aq) forming NH3 litmus paper blue
NH4+ +OH- NH3 + H2O
See flame tests on page 4 for more
cation tests
5. Formulae, equations and amounts of substance
The mole is the key concept for chemical calculations
DEFINITION: The mole is the amount of substance in grams that has the
same number of particles as there are atoms in 12 grams of carbon-12.
DEFINITION: Relative atomic mass is the average mass of one atom

Molar Mass for a compound can be calculated by adding

DEFINITION: Molar Mass is the mass in grams of 1 up the mass numbers(from the periodic table) of each
mole of a substance and is given the unit of g mol-1 element in the compound
eg CaCO3 = 40.1 + 12.0 +16.0 x3 = 100.1
For most calculations we will do at A-level we will use the following 3 equations
Learn these equations carefully and what units to use in them.
1. For pure solids, liquids and gases 2. For gases 3. For solutions
amount = mass Gas Volume (dm3)= amount x 24 Concentration = amount

MolarMass volume
This equation give the volume of a Unit of concentration: mol dm-3 or M
Unit of Mass: grams gas at room pressure (1atm) and
Unit of amount : mol Unit of Volume: dm3
room temperature 25oC. Converting volumes
It is usually best to give cm3 dm3 ÷ 1000

your answers to 3sf cm3 m3 ÷ 1000 000
dm3 m3 ÷ 1000
For pure solids, liquids and gases Example 1: What is the amount, in mol, in 35.0g of
CuSO4?
amount = mass
amount = mass/Mr
Mr
= 35/ (63.5 + 32 +16 x4)
Unit of Mass: grams = 0.219 mol
Unit of amount : mol
Many questions will involve changes of units

1000 mg =1g
1000 g =1kg
1000kg = 1 tonne
Significant Figures
Give your answers to the same
number of significant figures as the
Example 2: What is the amount, in mol, in 75.0mg of number of significant figures for the
CaSO4.2H2O? data you given in a question. If you
amount = mass/Mr are given a mixture of different
significant figures, use the smallest
= 0.075/ (40 + 32.0 +16.0 x4 + 18.0x2)
= 4.36x10-4 mol
Hydrated salt
A Hydrated salt contains water of crystallisation Example 3

Na2SO4 . xH2O has a molar mass of 322.1, Calculate
.
Cu(NO3)2 6H2O the value of x
hydrated copper (II) nitrate(V). Molar mass xH2O = 322.1 – (23x2 + 32.1 + 16x4)
= 180
Cu(NO3)2 X = 180/18
Anhydrous copper (II) nitrate(V). =10
This method could be used for measuring mass loss in various

Heating in a crucible thermal decomposition reactions and also for mass gain when
reacting magnesium in oxygen.
The lid improves the accuracy of the

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

50g, should not be used in this experiment as the
decomposition is like to be incomplete.
Small amounts the solid , such as
0.100 g, should not be used in
The crucible needs to be dry otherwise a wet crucible this experiment as errors in
would give an inaccurate result. It would cause mass loss weighing are too high.
to be too large as water would be lost when heating.
Example 4. 3.51 g of hydrated zinc sulphate were heated and 1.97 g

of anhydrous zinc sulphate were obtained.
Use these data to calculate the value of the integer x in ZnSO4.xH2O
Calculate the mass of H2O = 3.51 – 1.97 = 1.54g

Calculate moles Calculate moles = 1.54
= 1.97 of H2O
of ZnSO4 161.5 18
= 0.0122 =0.085
Calculate ratio of mole

of ZnSO4 to H2O = 0.0122 = 0.085
0.0122 0.0122
=7
=1
X=7
Avogadro's Constant
The mole is the amount of substance in Avogadro's Constant

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

Avogadro's Constant can be
1 mole of carbon dioxide molecules will contain 6.02 x 1023 molecules
used for atoms, molecules and
1 mole of sodium ions will contain 6.02 x 1023 ions
ions
No of particles = amount of substance (in mol) X Avogadro's constant
Example 5: How many atoms of Tin are Example 6 : How many chloride ions are there in a 25.0
there in a 6.00 g sample of Tin metal? cm3 of a solution of magnesium chloride of concentration
amount = mass/Ar 0.400 moldm-3 ?
= 6/ 118.7 amount= concentration x Volume
= 0.05055 mol MgCl2 = 0.400 x 0.025
Number atoms = amount x 6.02 x 1023 = 0.0100 mol

There are two moles of
= 0.05055 x 6.02 x 1023 Amount of chloride ions = 0.0100 x2 chloride ions for every
= 3.04 x1022 = 0.0200 one mole of MgCl2
Number ions of Cl- = amount x 6.02 x 1023
= 0.0200 x 6.02 x 1023
= 1.204 x1022
Density calculations are usually used with pure liquids but to work out the mass
Density
from a measured volume. It can also be used with solids and gases.
density = mass Density is usually given in g cm-3

Care needs to be taken if different units are
volume
used.
Example 7 : How many molecules of ethanol are there in a Example 8: There are 980mol of pure gold in a bar
0.500 dm3 of ethanol (CH3CH2OH) liquid ? The density of measuring 10 cm by 20 cm by 50 cm. What is the
ethanol is 0.789 g cm-3 density of gold in kg dm−3
Mass = amount x Mr
Mass = density x Volume
ethanol = 980 x 197
= 0.789 x 500
= 193060 g
= 394.5g
= 193.06kg
amount = mass/Mr
Volume = 10x20x50
= 394.5/ 46.0
= 10 000cm3
= 8.576 mol = 10dm3
Number of molecules= amount x 6.022 x 1023 density = mass/volume
= 8.576 x 6.022 x 1023 = 193/10
= 19.3 kg dm-3
= 5.16 x1024(to 3 sig fig)
Empirical Formula
Definition: An empirical formula is the simplest ratio of atoms of each element in the compound.
General method
The same method can be
Step 1 : Divide each mass (or % mass) by the atomic mass of the element used for the following types
Step 2 : For each of the answers from step 1 divide by the smallest one of of data:
those numbers. 1. masses of each element
in the compound
Step 3: sometimes the numbers calculated in step 2 will need to be multiplied
up to give whole numbers. 2. percentage mass of each
element in the compound
These whole numbers will be the empirical formula.
Example 9 : Calculate the empirical formula for a compound that contains

1.82g of K, 5.93g of I and 2.24g of O
Step1: Divide each mass by the atomic mass of the element
K = 1.82 / 39.1 I = 5.93/126.9 O = 2.24/16
= 0.0465 mol = 0.0467mol = 0.14 mol
Step 2 For each of the answers from step 1 divide by the smallest one of those numbers.
K = 0.0465/0.0465 I = 0.0467/0.0465 O = 0.14 / 0.0465
=1 =1 =3
Empirical formula =KIO3
Molecular formula from empirical formula
Definition: A molecular formula is the actual number of atoms of each element in the compound.
From the relative molecular mass (Mr) work out how many times the mass of the empirical
formula fits into the Mr.
Example 10 : work out the molecular formula for

the compound with an empirical formula of C3H6O The Mr does not need to be exact to turn an
and a Mr of 116 empirical formula into the molecular formula
because the molecular formula will be a
C3H6O has a mass of 58 whole number multiple of the empirical
formula
The empirical formula fits twice into Mr of 116
So molecular formula is C6H12O2
Concentration of Solutions
A solution is a mixture formed when a solute dissolves in a solvent. In chemistry we most commonly use
water as the solvent to form aqueous solutions. The solute can be a solid, liquid or a gas.
Molar concentration can be measured for solutions. This is calculated by dividing the amount in
moles of the solute by the volume of the solution. The volume is measure is dm3. The unit of molar
concentration is mol dm-3 ; it can also be called molar using symbol M
Concentration = amount Unit of concentration: mol dm-3 or M

volume Unit of Volume: dm3
Converting volumes
A m3 is equivalent to a cube A dm3 is equivalent to a cube A cm3 is equivalent to a cube

100cmx100cmx100cm= 1000000cm3 10cmx10cmx10cm= 1000cm3 1cmx1cmx1cm
1dm3 = 1litre 1cm3 = 1 ml
100cm
10cm
10cm 1cm
1cm
10cm 1cm
100cm
100cm 1cm3
1dm3 or 1 litre
1m3
1 m3 = 1000 dm3 or 1000L 1 dm3 = 1000 cm3 or 1000mL

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

cm3 m3 ÷ 1000 000
dm3 m3 ÷ 1000
Example 11 What is the concentration of solution Example 12 What is the concentration of solution
made by dissolving 5.00g of Na2CO3 in 250 cm3 water? made by dissolving 10kg of Na2CO3 in 0.50 m3 water?
amount = mass/Mr amount = mass/Mr
= 5 / (23.0 x2 + 12 +16 x3) = 10 000 / (23.0 x2 + 12 +16 x3)
= 0.0472 mol = 94.2 mol
conc= amount/Volume conc= amount/Volume
= 0.0472 / 0.25 = 94.2 / 500
= 0.189 mol dm-3 = 0.19 mol dm-3
Mass Concentration
The concentration of a solution can also be To turn concentration measured in mol dm-3 into
measured in terms of mass of solute per volume concentration measured in g dm-3 multiply by Mr of the
of solution substance
conc in g dm-3 = conc in mol dm-3 x Mr
Mass Concentration = mass The concentration in g dm-3 is the same as the mass of
volume solute dissolved in 1dm3
Unit of mass concentration: g dm-3

Unit of Mass g
Unit of Volume: dm3
Ions dissociating
When soluble ionic solids dissolve in water they will dissociate into separate ions. This can lead to the
concentration of ions differing from the concentration of the solute.
Example 13
If 5.86g (0.1 mol) of sodium chloride (NaCl) is dissolved in 1 dm3 of
water then the concentration of sodium chloride solution would be
0.1mol dm-3 . NaCl(s) +aq Na+(aq) + Cl- (aq)
However the 0.1mol sodium chloride would split up and form 0.1
mol of sodium ions and 0.1 mol of chloride ions. The concentration 0.1mol 0.1mol 0.1mol
of sodium ions is therefore 0.1 mol dm-3 and the concentration of
chloride ions is also 0.1 mol dm-3
Example 14
If 9.53g (0.1 mol) of magnesium chloride (MgCl2) is dissolved in 1
dm3 of water then the concentration of magnesium chloride solution
(MgCl2 aq) would be 0.1moldm-3 . MgCl2(s) +aq Mg2+(aq) + 2Cl- (aq)
However the 0.1mol magnesium chloride would split up and form
0.1mol 0.1mol 0.2mol
0.1 mol of magnesium ions and 0.2 mol of chloride ions. The
concentration of magnesium ions is therefore 0.1 mol dm-3 and the
concentration of chloride ions is now 0.2 mol dm-3
Making a solution
• Weigh the sample bottle containing the required mass of Alternatively the known mass of
solid on a 2 dp balance solid in the weighing bottle could be
• Transfer to beaker and reweigh sample bottle transferred to beaker, washed and
• Record the difference in mass washings added to the beaker.
• Add 100cm3 of distilled water to the beaker. Use a glass

rod to stir to help dissolve the solid.
•Sometimes the substance may not dissolve well in cold

water so the beaker and its contents could be heated gently
until all the solid had dissolved.
• Pour solution into a 250cm3 graduated flask via a funnel. Remember to fill so the bottom of the
• Rinse beaker and funnel and add washings from the meniscus sits on the line on the neck of
beaker and glass rod to the volumetric flask. the flask. With dark liquids like potassium
• make up to the mark with distilled water using a dropping manganate it can be difficult to see the
pipette for last few drops. meniscus.
• Invert flask several times to ensure uniform solution.
Dilutions
Diluting a solution
Using a volumetric pipette is more
accurate than a measuring cylinder
•Pipette 25cm3 of original solution into a 250cm3 because it has a smaller uncertainty
volumetric flask
•make up to the mark with distilled water using a Use a teat pipette to make up to the mark
dropping pipette for last few drops. in volumetric flask to ensure volume of
• Invert flask several times to ensure uniform solution. solution accurately measured and one
doesn’t go over the line
Calculating Dilutions
Diluting a solution will not change the amount of moles of solute present but increase the volume of
solution and hence the concentration will lower
amount= volume x concentration
If amount of moles does not change then
Original volume x original concentration = new diluted volume x new diluted concentration
so new diluted concentration = original concentration x Original volume

new diluted volume
The new diluted volume will be equal to the original volume of solution added + the volume of water added.
Example 15
If 50 cm3 of water are added to 150 cm3 of a 0.20 mol dm-3 NaOH solution, what will the concentration of
the diluted solution be?
new diluted concentration = original concentration x Original volume
new diluted volume
new diluted concentration = 0.20 x 0.150
0.200
= 0.15 mol dm-3
Example 16
What volume of water in cm3 must be added to dilute 5.00 cm3 of 1.00 mol dm−3 hydrochloric acid so that
it has a concentration of 0.050 mol dm−3 ?
Amount in mol original solution = conc x vol
= 1.00 x 0.005
= 0.005
New volume = amount /conc
= 0.005/0.05
= 0.1dm3 = 100cm3
Volume of water added = 100-5 = 95cm3
Ideal Gas Equation
The ideal gas equation applies to all gases and mixtures of PV = nRT
gases. If a mixture of gases is used the value n will be the total
moles of all gases in the mixture. Unit of Pressure (P):Pa
Unit of Volume (V): m3
The biggest problems students have with this equation is choosing Unit of Temp (T): K
and converting to the correct units, so pay close attention to the units. n= moles
R = 8.31 JK–1mol–1
Example 17: What is the mass of Cl2 gas that has a pressure of Converting temperature
100kPa, temperature 20oC , volume 500cm3. (R = 8.31)
oC K add 273
moles = PV/RT
100 kPa = 100 000 Pa
= 100 000 x 0.0005 / (8.31 x 293) 20oC = 20+273= 293K
= 0.0205 mol 500 cm3 = 0.0005 m3
Mass = amount x Mr
= 0.0205 x (35.5 x2)
= 1.46 g
Example 18: 0.150g of a volatile liquid was injected into a sealed gas syringe. The gas syringe was placed in an oven at
70oC at a pressure of 100kPa and a volume of 80cm3 was measured. What is the Mr of the volatile liquid ? (R = 8.31)
moles = PV/RT 100 kPa = 100 000 Pa

= 100 000 x 0.00008 / (8.31 x 343) 80 cm3 = 0.00008 m3
= 0.00281 mol
Mr = mass/amount
= 0.15 / 0.00281
= 53.4 g mol-1
Using a gas syringe
Gas syringes can be used for a variety of experiments where the volume of a gas is measured, possibly to
work out moles of gas or to follow reaction rates.
The volume of a gas depends on pressure Make sure you don’t leave
and temperature so when recording volume gaps in your diagram where
it is important to note down the temperature gas could escape
and pressure of the room.
Moles of gas can be calculated from gas

volume (and temperature and pressure)
using ideal gas equation PV = nRT
If drawing a gas syringe make

Potential errors in using a gas syringe
sure you draw it with some
•gas escapes before bung inserted
measurement markings on the
•syringe sticks
barrel to show measurements
• some gases like carbon dioxide or sulphur
can be made.
dioxide are soluble in water so the true amount of
gas is not measured.
Changing the Conditions of a gas
Questions may involve the same amount of gas under different conditions.
Example 19
40 cm3 of oxygen and 60 cm3 of carbon dioxide, each at 298 K and 100 kPa, were placed into an
evacuated flask of volume 0.50 dm3. What is the pressure of the gas mixture in the flask at 298 K?
There are two approaches to solving this

1. Work out amount in mol of gas using ideal gas equation then put back into ideal gas
equation with new conditions
P1V1 = P2V2
2. Or combine the equation n= PV/RT as on right
T1 T2
Can do this as moles of gas do not change
As Temperature is the same can make the above equation P1V1 = P2V2
P2 = P1V1 /V2
= 100000 x 1x 10-4 / 5x10-4
= 20 000Pa
Reacting Volumes of Gas
Equal volumes of any gases measured under the same 1 mole of any gas at room
conditions of temperature and pressure contain equal pressure (1atm) and room
numbers of molecules (or atoms if the gas in monatomic) temperature 25oC will have the
volume of 24dm3
Volumes of gases reacting in a balanced equation
can be calculated by simple ratio
Example 20 If one burnt 500 cm3 of methane at 1atm and 300K what volume of
Oxygen would be needed and what volume of CO2 would be given off under the
same conditions?
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(l)
1 mole 2 mole 1 mole
500cm3 1dm3 500cm3
Simply multiply
gas volume x2
Example 21 An important reaction which occurs in the catalytic converter of a car is

2CO(g) + 2NO(g) 2CO2(g) + N2(g)
In this reaction, when 500 cm3 of CO reacts with 500 cm3 of NO at 650 °C and at 1 atm.
Calculate the total volume of gases produced at the same temperature and pressure ?
2CO(g) + 2NO(g) 2CO2(g) + N2(g) total volume of gases produced = 750cm3

500cm3 500cm3 500cm3 250cm3
Converting quantities between different substances using a balanced equation Typically we are given a quantity
of one substance and are asked
N2 + 3H2 2NH3 to work out a quantity for
another substance in the
The balancing (stoichiometric) numbers are mole ratios reaction. Any of the above three
e.g. 1 mol of N2 reacts with 3 mol of H2 to produce 2mol of NH3 equations can be used.
Step 3
Step 1:
Step 2: Convert amount, in mol, of
Use one of the above 3 equations to
Use balanced equation to second substance into quantity
convert any given quantity into
convert amount in mol of initial question asked for using
amount in mol
substance into amount in mol of relevant equation
Mass amount
second substance e.g. amount ,Mr mass
Volume of gas amount
Amount gas vol gas
Conc and vol of solution amount
amount, vol solution conc
Example 22: What mass of Carbon dioxide would be Example 23: What mass of Copper would react completely
produced from heating 5.50 g of sodium with 150 cm3 of 1.60M nitric acid?
hydrogencarbonate? 3Cu + 8HNO3 3Cu(NO3 )2 + 2NO + 4H2O
2NaHCO3 Na2CO3 + CO2 + H2O
Step 1: work out moles of nitric acid
Step 1: work out amount, in mol, of sodium
amount = conc x vol
hydrogencarbonate
= 1.6 x 0.15
amount = mass / Mr
= 0.24 mol
= 5.5 /84
= 0.0655 mol
Step 2: use balanced equation to give moles of Cu
Step 2: use balanced equation to give amount in mol 8 moles HNO3 : 3 moles Cu
of CO2 So 0.24 HNO3 : 0.09 (0.24 x 3/8) mol Cu
2 moles NaHCO3 : 1 moles CO2
So 0.0655 HNO3 : 0.0328mol CO2
Step 3: work out mass of Cu
Step 3: work out mass of CO2 Mass = amount x Mr
Mass = amount x Mr = 0.09 x 63.5
= 0.0328 x 44.0 =5.71g
=1.44g
Example 24: What is the total volume of gas produced in Example 25: 23.6cm3 of H2SO4 neutralised 25.0cm3 of 0.150M
dm3 at 333K and 100kPa when 0.651 g of magnesium NaOH. What is the concentration of the H2SO4?
nitrate decomposes when heated? H2SO4 + 2NaOH Na2SO4 +2H2O
2Mg (NO3)2 (s) 2 MgO (s) + 4NO2 (g) + O2 (g)
Step 1: work out moles of magnesium nitrate Step 1: work out moles of sodium hydroxide
Moles = mass / Mr amount = conc x vol
= 0.651 / 148.3 = 0.150 x 0.025
= 0. 00375 mol
= 0.00439 mol
Step 2: use balanced equation to give moles of gas Step 2: use balanced equation to give moles of H2SO4
produced 2 moles NaOH : 1 moles H2SO4
2 moles Mg (NO3)2 : 4NO2 (g) + O2 (g) ie 5moles of gas So 0.00375 NaOH : 0.001875 mol H2SO4
So 0.00439 Mg (NO3)2 : 0.01098( 0.00439 x 5/2) moles
gas Step 3 work out concentration of H2SO4
conc= amount/Volume
Step 3: work out volume of gas
= 0.001875 / 0.0236
Volume = nRT/P
= (0.01098 x 8.31 x 333 )/ 100000 = 0.0794 mol dm-3
= 0.000304m3
= 0.303dm3
Titrations
The method for carrying out the titration Safety precautions
•rinse equipment (burette with acid, pipette with alkali, conical Acids and alkalis are corrosive
flask with distilled water) (at low concentrations acids are
•pipette 25 cm3 of alkali into conical flask irritants)
•touch surface of alkali with pipette ( to ensure correct amount Wear eye protection and gloves
is added) If spilled immediately wash affected
•adds acid solution from burette parts after spillage
•make sure the jet space in the burette is filled with acid
•add a few drops of indicator and refer to colour change at end If substance is unknown treat it as
point potentially toxic and wear gloves.
•phenolphthalein [pink (alkali) to colourless (acid): end point pink
colour just disappears] [use if NaOH is used]
•methyl orange [yellow (alkali) to red (acid): end point orange] A conical flask is used in preference
[use if HCl is used] to a beaker because it is easier to
•use a white tile underneath the flask to help observe the colour swirl the mixture in a conical flask
change without spilling the contents.
•add acid to alkali whilst swirling the mixture and add acid
dropwise at end point Distilled water can be added to the
•note burette reading before and after addition of acid conical flask during a titration to wash
•repeats titration until at least 2 concordant results are the sides of the flask so that all the
obtained- two readings within 0.1 of each other acid on the side is washed into the
reaction mixture to react with the alkali.
There will be a small amount of the liquid left in the pipette when It does not affect the titration reading
it has been emptied. Do not force this out. The pipette is as water does not react with the
calibrated to allow for it. reagents or change the number of
moles of acid added.
If the jet space in the burette is not filled properly prior to
commencing the titration it will lead to errors if it then fills Only distilled water should be used to
during the titration, leading to a larger than expected titre wash out conical flasks between
reading. titrations because it does not add and
extra moles of reagents
Working out average titre results
Only make an average of the concordant titre results
lf 2 or 3 values are within 0.10cm3

Recording results
and therefore concordant or close
•Results should be clearly recorded in a table
then we can say results are accurate
•Result should be recorded in full (i.e. both initial and final
and reproducible and the titration
readings)
technique is good/ consistent
•Record titre volumes to 2dp (0.05 cm3)
Titrating mixtures
Testing batches If titrating a mixture to work out the concentration
In quality control it will be necessary to do of an active ingredient it is necessary to consider
titrations/testing on several samples as the if the mixture contains other substances that
amount/concentration of the chemical being tested may have acid base properties.
vary between samples. If they don’t have acid base properties we can
titrate with confidence.
11
More complicated titration calculations- taking samples
Example 26: A 25.0cm3 sample of vinegar was diluted in a Common Titration Equations
250cm3 volumetric flask. This was then put in a burette and
23.10cm3 of the diluted vinegar neutralised 25.0 cm3 of 0.100 CH3CO2H + NaOH CH3CO2-Na+ + H2O
M NaOH. What is the concentration of the vinegar in gdm-3 ?
H2SO4 + 2NaOH Na2SO4 +2H2O
CH3CO2H + NaOH CH3CO2-Na+ + H2O
HCl + NaOH NaCl +H2O
Step 1: work out amount, in mol, of sodium hydroxide
amount = conc x vol
NaHCO3 + HCl NaCl + CO2 + H2O
= 0.10 x 0.025 Na2CO3 + 2HCl 2NaCl + CO2 + H2O
= 0. 00250 mol
Step 2: use balanced equation to give moles of CH3CO2H Example 28
1 moles NaOH : 1 moles CH3CO2H 950 mg of impure calcium carbonate tablet was crushed. 50.0
So 0.00250 NaOH : 0.00250 moles CH3CO2H cm3 of 1.00 mol dm–3 hydrochloric acid, an excess, was then
added. After the tablet had reacted, the mixture was
Step 3 work out concentration of diluted CH3CO2H in 23.1 transferred to a volumetric flask. The volume was made up to
(and 250 cm3)in moldm-3 exactly 100 cm3 with distilled water. 10.0 cm3 of this solution
conc= amount/Volume was titrated with 11.1cm3 of 0.300 mol dm–3 sodium
hydroxide solution.
= 0.00250 / 0.0231 What is the percentage of CaCO3 by mass in the tablet?
= 0.108 mol dm-3 1. Calculate the number of moles of sodium hydroxide used
Step 4 work out concentration of original concentrated amount = conc x vol
CH3CO2H in 25cm3 in moldm-3 = 0.30 x 0.0111
conc = 0.108 x 10 = 1.08 mol dm-3 = 0. 00333 mol
Step 5 work out concentration of CH3CO2H in original 2. Work out number of moles of hydrochloric acid left in 10.0 cm3
concentrated 25 cm3 in gdm-3 use balanced equation to give moles of HCl
conc in gdm-3 = conc in mol dm-3 x Mr 1 mol NaOH : 1 mol HCl
So 0.00333 NaOH : 0.00333 moles HCl
= 1.08 x 60 = 64.8 g dm-3
3. Calculate the number of moles of hydrochloric acid left in
100 cm3 of solution
Example 27. An unknown metal carbonate reacts with
hydrochloric acid according to the following equation. Moles in 100cm3 = 0.00333 x10
M2CO3(aq) + 2HCl(aq) 2MCl(aq) + CO2(g) + H2O(l) =0.0333
A 3.96 g sample of M2CO3 was dissolved in distilled water to
make 250 cm3 of solution. A 25.0 cm3 portion of this solution 4. Calculate the number of moles of HCl that reacted with
required 32.8 cm3 of 0.175 mol dm–3 hydrochloric acid for the indigestion tablet.
complete reaction. Calculate the Mr of M2CO3 and identify the
In original HCl 50.0 cm3 of 1.00 mol dm–3 there are 0.05mol
metal M
1. Calculate the number of moles of HCl used moles of HCl that =0.05 -0.0333
amount = conc x vol reacted with the =0.0167
= 0.175 x 0.0328 indigestion tablet.
= 0. 00574 mol
2. Work out number of moles of M2CO3 in 25.0 cm3 put in conical 5 Use balanced equation to give moles of CaCO3
flask CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)
use balanced equation to give moles of M2CO3 2 mol HCl : 1 mol CaCO3
2 mol HCl : 1 mol M2CO3 So 0.0167 HCl : 0.00835 moles CaCO3
So 0. 00574 NaOH : 0.00287 moles M2CO3
6. work out the mass of CaCO3 in original tablet
3. Calculate the number of moles M2CO3 acid in original 250 cm3
of solution mass= amount x Mr
Moles in 250cm3 = 0.00287 x10 = 0.00835 x 100 = 0.835 g
=0.0287
percentage of
4. work out the Mr of M2CO3 = 0.835/0.950 x100
CaCO3 by mass in
Mr= mass / amount the tablet
= 87.9 %
= 3.96/ 0.0287= 138.0
5. Work out Ar of M = (138-12- 16x3)
2
Ar of M = 39 M= potassium
Uncertainty
Readings and Measurements
Readings Measurements The uncertainty of a reading (one judgement) is at
the values found from a the values taken as the least ±0.5 of the smallest scale reading.
single judgement when difference between the The uncertainty of a measurement (two
using a piece of equipment judgements of two judgements) is at least ±1 of the smallest scale
values (e.g. using a reading.
burette in a titration)
Calculating Apparatus Uncertainties

Each type of apparatus has a sensitivity uncertainty To decrease the apparatus uncertainties
you can either decrease the sensitivity
•balance ± 0.001 g uncertainty by using apparatus with a
•volumetric flask ± 0.1 cm3 greater resolution (finer scale divisions )
•25 cm3 pipette ± 0.1 cm3 or you can increase the size of the
•burette ± 0.05 cm3 measurement made.
Calculate the percentage error for each piece of equipment used by Uncertainty of a measurement using
a burette. If the burette used in the
% uncertainty = ± uncertainty x 100 titration had an uncertainty for each
Measurement made on apparatus reading of +/– 0.05 cm3 then during a
titration two readings would be taken
e.g. for pipette so the uncertainty on the titre volume
% uncertainty = 0.05/ 25 x100 would be +/– 0.10 cm3 .
To calculate the maximum percentage apparatus uncertainty in the

final result add all the individual equipment uncertainties together.
Reducing uncertainties in a titration If looking at a series of measurements

in an investigation the experiments
Replacing measuring cylinders with pipettes or burettes which have with the smallest readings will have
lower apparatus uncertainty will lower the error the highest experimental uncertainties.
To reduce the uncertainty in a burette reading it is necessary to

make the titre a larger volume. This could be done by: increasing
the volume and concentration of the substance in the conical flask
or by decreasing the concentration of the substance in the burette.
Reducing uncertainties in measuring mass

Using a more accurate balance or a larger mass will
reduce the uncertainty in weighing a solid
Weighing sample before and after addition and then
calculating difference will ensure a more accurate
measurement of the mass added.
If the %uncertainty due to the apparatus <

percentage difference between the actual value
Calculating the percentage difference between the
and the calculated value then there is a
actual value and the calculated value
discrepancy in the result due to other errors.
If we calculated an Mr of 203 and the real value is 214,
then the calculation is as follows: If the %uncertainty due to the apparatus >
Calculate difference 214-203 = 11 percentage difference between the actual value
% = 11/214 x100 and the calculated value then there is no
=5.41% discrepancy and all errors in the results can be
explained by the sensitivity of the equipment.
% Yield
% yield in a process can be lowered through
actual yield incomplete reactions, side reactions, losses during
percentage yield = x 100 transfers of substances, losses during purification
theoretical yield stages.
Example 29: 25.0g of Fe2O3 was reacted and it produced 10.0g of Fe. What is the percentage yield?
Fe2O3 + 3CO 2Fe + 3 CO2
First calculate maximum mass of Fe that could be produced

Step 1: work out amount in mol of Iron oxide
amount = mass / Mr
=25 / 159.6
= 0.1566 mol
Step 2: use balanced equation to give moles of Fe

1 moles Fe2O3 : 2 moles Fe
So 0.1566 Fe2O3 : 0.313moles Fe
% yield = (actual yield/theoretical yield) x 100
Step 3: work out mass of Fe
Mass = amount x Mr = (10/ 17.48) x 100
= 0.313 x 55.8
=57.2%
=17.5g
% Atom Economy
Mass of useful products Do take into account

percentage balancing numbers
= x 100
atom economy when working out %
Mass of all reactants
atom economy.
Example 30: What is the % atom economy for the following reaction where Fe is
the desired product assuming the reaction goes to completion?
Fe2O3 + 3CO 2Fe + 3 CO2
% atom economy = (2 x 55.8)
x 100
(2 x 55.8 + 3x16) + 3 x (12+16)
=45.8%
Sustainable chemistry requires chemists to design Reactions where there is only one product where all
processes with high atom economy that minimise atoms are used making product are ideal and have
production of waste products. 100% atom economy.
e.g. CH2=CH2 + H2 CH3CH3
If a process does have a side, waste product the economics of the process can be improved by selling the
bi-product for other uses
Reactions of Acids
Neutralisation reactions form salts
A Salt is formed when the H+ ion of an acid is replaced
by a metal ion or an ammonium ion Bases neutralise acids. Common bases are
metal oxides, metal hydroxides and ammonia.
The most common strong acids are : An Alkali is a soluble base that releases OH-
Hydrochloric ( HCl), sulphuric (H2SO4) and nitric ions in aqueous solution;
(HNO3) acid; The most common alkalis are sodium hydroxide
(NaOH), potassium hydroxide (KOH) and
aqueous ammonia (NH3)
Common Acid Reaction Equations
Acid + Carbonate Salt + Water + Carbon Dioxide
ACID + BASE SALT + WATER
H2SO4 + K2CO3 K2SO4 + CO2 + H2O
HCl + NaOH NaCl +H2O
2HCl + Na2CO3 2NaCl + CO2 + H2O
2HNO3 + Mg(OH)2 Mg(NO3)2 + 2H2O
H2SO4 + 2NaOH Na2SO4 +2H2O 2HCl + CaCO3 CaCl2 + CO2 + H2O
2HCl + CaO CaCl2 +H2O Observations : In carbonate reactions there will

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

2HCl + Mg MgCl2 + H2
Observations: These reaction will

effervesce because H2 gas is evolved
and the metal will dissolve
Ionic equations for reactions of acids with metals, carbonates, bases and alkalis
Ionic Equations
acid + metal salt + hydrogen
2HCl (aq) + Mg (s) MgCl2 (aq) + H2 (g) 2H+ (aq) + Mg (s) Mg2+ (aq) + H2 (g)
acid + alkali (NaOH) salt + water

2HNO2 (aq) + Ba(OH)2 (aq) Ba(NO2)2 (aq) + 2H2O (l) H+ (aq) + OH– (aq) H2O (l)
acid + carbonate (Na2CO3) salt + water + CO2

2H+(aq) + CO3 2–(aq) H2O (l) + CO2 (g)
2HCl (aq)+ Na2CO3 (aq) 2NaCl (aq) + H2O (l)+ CO2 (g)
Example 22
The equation representing the reaction between copper(II) oxide and dilute sulfuric acid is
CuO(s) + H2SO4(aq) CuSO4(aq) + H2O(l)
What is the ionic equation?
Only sulphate ion is a spectator ion in this case because it’s the only ion not changing state
CuO(s) + 2H+ Cu2+ (aq) + H2O(l)
Displacement Reactions
Metal displacement reactions
More reactive metals will displace less reactive metals from their compounds
Mg + CuSO4 Cu + MgSO4
Ionically Mg + Cu2+ Cu + Mg2+
Halogen displacement reactions
A halogen that is a strong oxidising agent will displace a halogen that has a lower oxidising
power from one of its compounds
Cl2(aq) + 2Br – (aq) 2Cl – (aq) + Br2(aq)

See topic 4b Halogens for
Cl2(aq) + 2I – (aq) 2Cl – (aq) + I2(aq)
more detail
Br2(aq) + 2I – (aq) 2Br – (aq) + I2(aq)
Precipitation Reactions
Insoluble salts can be made by mixing appropriate solutions of ions so that a precipitate is formed
Lead nitrate (aq) + sodium chloride (aq) lead chloride (s) + sodium nitrate (aq)
These are called precipitation reactions. A precipitate is a solid
When making an insoluble salt, normally the salt would be removed by filtration, washed with
distilled water to remove soluble impurities and then dried on filter paper
Writing Ionic equations for precipitation reactions
We usually write ionic equations to show precipitation Spectator ions are ions that are not
reactions. Ionic equations only show the ions that are • Not changing state
reacting and leave out spectator ions. • Not changing oxidation number
Take full equation Pb(NO3)2 (aq) + 2NaCl (aq) PbCl2 (s) + 2 NaNO3 (aq)
Separate (aq) solutions Pb2+(aq) + 2NO3-(aq) + 2Na+ (aq)+ 2Cl-(aq) PbCl2 (s) + 2 Na+(aq)+ 2NO3- (aq)
into ions
Cancel out spectator ions

Pb2+(aq) + 2Cl-(aq) PbCl2 (s)
leaving ionic equation
Hazards and Risks
A hazard is a substance or procedure that can has the RISK: This is the probability or chance that
potential to do harm. harm will result from the use of a
Typical hazards are toxic/flammable /harmful/ hazardous substance or a procedure
irritant /corrosive /oxidizing/ carcinogenic
In the laboratory we try to minimise the risk
Irritant - dilute acid and alkalis- wear googles Hazardous substances in low
Corrosive- stronger acids and alkalis wear goggles concentrations or amounts
Flammable – keep away from naked flames will not pose the same risks
Toxic – wear gloves- avoid skin contact- wash hands after use as the pure substance.
Oxidising- Keep away from flammable / easily oxidised materials
Safely dealing with excess acid

Sodium hydrogen carbonate (NaHCO3) and calcium carbonate (CaCO3) are good for neutralising excess
acid in the stomach or acid spills because they are not corrosive and will not cause a hazard if used in
excess. They also have no toxicity if used for indigestion remedies but the CO2 produced can cause wind.
Magnesium hydroxide is also suitable for dealing with excess stomach acid as it has low solubility in water
and is only weakly alkaline so not corrosive or dangerous to drink (unlike the strong alkali sodium
hydroxide). It will also not produce any carbon dioxide gas.
17
7. Mass spectra and IR
7A Mass spectrometry
Measuring the Mr of an organic molecule Spectra for C4H10
If a molecule is put through a mass spectrometer Mass spectrum for butane

it will often break up and give a series of peaks
caused by the fragments. The peak with the 43
Molecular ion
largest m/z, however, will be due to the complete
C4H10+
molecule and will be equal to the Mr of the
molecule. This peak is called the parent ion or 29
molecular ion
58
Fragmentation
Molecular ion formed: M → [M]+. + e–
When organic molecules are passed through a mass
spectrometer, it detects both the whole molecule and The molecule loses an electron and
fragments of the molecule. becomes both an ion and a free radical
Several peaks in the mass spectrum occur due to fragmentation. This process produces an ion
The Molecular ion fragments due to covalent bonds breaking: [M]+. → X+ + Y. and a free radical. The ion is
responsible for the peak
Relatively stable ions such as carbocations R+ such as CH3CH2+ and
acylium ions [R-C=O]+ are common. The more stable the ion, the greater
the peak intensity.
The peak with the highest mass/charge ratio will be normally due to the
original molecule that hasn’t fragmented (called the molecular ion) . As
the charge of the ion is +1 the mass/ charge ratio is equal to Mr.
Equation for formation molecular ion

Mass spectrum for propanal
CH3CH2CHO → [CH3CH2CHO]+. + e– m/z 58
29 [CHO]+
Equations for formation of fragment ions from molecular ions
58
[CH3CH2CHO]+. → [CHO]+ + .CH2CH3 m/z 29
[CH3CH2CHO]+.
[CH3CH2CHO]+. → [CH3CH2]+ + .CHO m/z 29

Mass spectrum for propanone
CH3COCH3 → [CH3COCH3]+. + e– m/z 58
The high peak 43
at 43 due to [CH3CO]+ Equations for formation of fragment ions from molecular ions
stability of acyl
group [CH3COCH3]+. → [CH3CO]+ + . CH3 m/z 43
[CH3COCH3]+.
58
15 It is not possible for propanone to fragment to give a
peak at 29 so the fragmentation patterns can distinguish
between the structural isomers of propanone and
propanal
7B Infrared spectroscopy
Certain bonds in a molecule absorb infra-red radiation at Complicated spectra can be obtained than
characteristic frequencies causing the covalent bonds to provide information about the types of bonds
vibrate present in a molecule
ABOVE 1500 cm-1 – “Functional group identification”

BELOW 1500 cm-1 – “Fingerprinting”
Complicated and contains many

signals – picking out functional
group signals difficult.
This part of the spectrum is unique

for every compound, and so can be
used as a "fingerprint".
e.g. C=O 1640 – 1750 cm-1 A computer will compare the IR

O-H (acid) 2500- 3300 cm-1 spectra against a database of
known pure compounds to identify
the compound
Use an IR absorption table provided in

exam to deduce presence or absence
of particular bonds or functional groups
Use spectra to identify particular functional groups e.g. an alcohol from

Bond Wavenumber an absorption peak of the O–H bond, or C=O stretching absorption in
aldehydes and ketones
C-O 1000-1300
C=O 1640-1750 Spectra for

butanal
C-H 2850 -3100
O
O-H 2500-3300
Carboxylic acids Very broad H3C CH2 CH2 C
H
N-H 3200-3500
O-H 3200- 3550 2000 1500

Acohols, phenols broad C=O
Absorption or trough in between 1640-1750 cm-1 range indicates
presence of C=O bond
Always quote the wave number range from the data sheet
Spectra for
O-H absorptions tend ethanoic acid
to be broad
O
Absorption or trough in
between 2500-3300 cm-1 range H3C C
indicates presence of O-H OH
bond in an acid
C=O
Absorption or trough in between 1640-
1750 cm-1 range indicates presence of
C=O bond
Molecules which change their polarity as they vibrate can

absorb infrared radiation. E.g. C-H, C=O, O-H
Molecules such as H2, O2 and N2 cannot change their polarity as they vibrate
so can absorb infrared radiation and don’t register on an infra red spectrum
The absorption of infra-red radiation by bonds in this type of spectroscopy is the same absorption
that bonds in CO2, methane and water vapour in the atmosphere do that cause them to be
greenhouse gases.
H2O, CO2, CH4 and NO molecules absorb IR radiation

and are greenhouse gases, whilst O2 and N2 are not.
8. Energetics I
Definition: Enthalpy change is the amount of heat energy
taken in or given out during any change in a system provided the
pressure is constant.
If an enthalpy change occurs then energy is
In an exothermic change energy is transferred from transferred between system and
the system (chemicals) to the surroundings. surroundings . The system is the
chemicals and the surroundings is
The products have less energy than the reactants everything outside the chemicals.
In an endothermic change, energy is

Energy
Activation transferred from the surroundings to the

Energy: system (chemicals). They require an input of
EA heat energy e.g. thermal decomposition of
reactants calcium carbonate
The products have more energy than the
reactants
∆H
products
Activation
Energy:
Progress of Reaction EA
Energy
In an exothermic reaction the

∆H is negative reactants ∆H
Common oxidation exothermic processes are the In an endothermic reaction

combustion of fuels and the oxidation of the ∆H is positive
carbohydrates such as glucose in respiration
Progress of Reaction
Standard enthalpy change of formation
The standard enthalpy change of formation of a compound is the Mg (s) + Cl2 (g)  MgCl2 (s)
enthalpy change when 1 mole of the compound is formed from 2Fe (s) + 1.5 O2 (g)  Fe2O3 (s)
its elements under standard conditions (298K and 100kpa), all
reactants and products being in their standard states The enthalpy of formation
Symbol fH of an element = 0 kJ mol-1
Standard enthalpy change of combustion
The standard enthalpy of combustion of a substance is defined as CH4 (g) + 2O2 (g) CO2 (g) + 2 H2O (l)
the enthalpy change that occurs when one mole of a substance is
combusted completely in oxygen under standard conditions. Incomplete combustion will lead to
(298K and 100kPa), all reactants and products being in their soot (carbon), carbon monoxide and
standard states water. It will be less exothermic than
complete combustion.
Symbol cH
When an enthalpy change is
Enthalpy changes are normally quoted at standard conditions.
measured at standard
Standard conditions are : conditions the symbol is
• 100 kPa pressure used
• 298 K (room temperature or 25oC) Eg H
• Solutions at 1mol dm-3
• all substances should have their normal state at 298K
Definition: Enthalpy change of reaction is the enthalpy change
when the number of moles of reactants as specified in the
balanced equation react together
Enthalpy change of Neutralisation

The standard enthalpy change of neutralisation is the enthalpy change when solutions of an
acid and an alkali react together under standard conditions to produce 1 mole of water.
Enthalpy changes of neutralisation are always exothermic. For reactions involving strong
acids and alkalis, the values are similar, with values between -56 and -58 kJ mol-1
Hess’s Law
Hess’s law is a version of the first law
Hess’s law states that total enthalpy change for a reaction is of thermodynamics, which is that
independent of the route by which the chemical change takes place energy is always conserved.
2H (g) + 2Cl(g)
On an energy level diagram the directions of the arrows can
show the different routes a reaction can proceed by
a
In this example one route is arrow ‘a’
H2 + Cl2 b The second route is shown by arrows ΔH plus arrow ‘b’
ΔH So a = ΔH + b
2HCl (g) And rearranged
ΔH = a - b
ΔH
H+ (g) + Br - (g) H+ (aq) + Br - (aq) Interconnecting reactions can also be
shown diagrammatically.
a
d
In this example one route is arrow ‘a’ plus ΔH
The second route is shown by arrows ‘c’ plus arrow ‘d’
H (g) + Br (g) HBr (g)
c So a+ ΔH = c + d
And rearranged
ΔH = c + d - a
2
Often Hess’s law cycles are used to measure the enthalpy change for a reaction that cannot be measured
directly by experiments. Instead alternative reactions are carried out that can be measured experimentally.
H reaction This Hess’s law is used to work out the

CuSO4 (s) + 5H2O (l) CuSO4.5H2O (s) enthalpy change to form a hydrated salt
from an anhydrous salt.
-66.1 kJmol-1 + aq + aq +11kJmol-1

This cannot be done experimentally
because it is impossible to add the
CuSO4 (aq) exact amount of water and it is not easy
to measure the temperature change of
a solid.
H reaction + 11kJmol-1 = -66.1 kJmol-1
Instead both salts are dissolved in excess
H reaction = -66.1 - 11
water to form a solution of copper sulphate.
= -77.1 kJmol-1 The temperature changes can be measured
for these reactions.
H reaction This Hess’s law is used to work out the

CaCO3 (s) CaO (s) + CO2 (g) enthalpy change for the thermal
decomposition of calcium carbonate.
ΔH1 ΔH2
(+2HCl) (+2HCl)
This cannot be done experimentally
because it is impossible to add the add
CaCl2 (aq) + H2O (l) + CO2 (g) the heat required to decompose the
solid and to measure the temperature
change of a solid at the same time.
H reaction + ΔH2 = ΔH1
H reaction = ΔH1 - ΔH2 Instead both calcium carbonate and calcium

oxide are reacted with hydrochloric acids to
form a solution of calcium chloride. The
temperature changes can be measured for
these reactions.
Using Hess’s law to determine enthalpy changes from enthalpy changes of formation.
H reaction
Reactants Products
H reaction = Σ fH products - Σ fH reactants
Σ fH reactants Σ fH products
Elements in standard states
Example 1. What is the enthalpy change for this reaction ?

Al2O3 + 3 Mg  3 MgO + 2 Al H reaction
Remember Al2O3 (s) + 3 Mg (s) 3 MgO (s) + 2 Al (s)
H = ΣfH products – Σ fH reactants elements have
Hf = 0 fH(Al2O3) 3 x fH (MgO)
H = 3 x fH (MgO) – fH (Al2O3)
H = (3 x –601.7) – –1675.7 fH(MgO)= -601.7 kJ mol-1 2Al (s) + 3 Mg (s) + 1.5O2 (g)
= -129.4 kJ mol-1 fH(Al2O3) = -1675.7 kJ mol-1
Example 2. Using the following data to calculate the heat of combustion of propene
Hf C3H6(g) = +20 kJ mol-1 Hf CO2(g)= –394 kJ mol-1 Hf H2O(g)= –242 kJ mol-1
C3H6 + 4.5 O2  3CO2 + 3H2O
 cH
C3H6 (g) + 4.5 O2 (g) 3 CO2 (g) + 3 H2O (g)
cH = Σ fH products – Σ fH reactants
cH = [3 x fH (CO2) + 3 x fH (H2O)] - fH (C3H6) 3 x fH (CO2)
fH(C3H6) 3 x fH (H2O)
cH = [(3 x –394) + (3 x –242)] – 20
= -1928 kJ mol-1 3C (s) + 3 H2 (g) + 4.5 O2 (g)
Using Hess’s law to determine enthalpy changes from enthalpy changes of combustion.
H reaction
Reactants Products
H reaction = Σ cH reactants - Σ cH products Σ cH reactants

+O2 +O2
Σ cH products
Combustion Products
Example 3. Using the following combustion data to calculate the heat of reaction
CO (g) + 2H2 (g)  CH3OH (g)
cH CO(g) = -283 kJ mol cH H2 (g)= –286 kJ mol-1 cH CH3OH(g)= –671 kJ mol-1
-1
H reaction
H reaction = Σ cH reactants - Σ cH products CO (g) + 2H2(g) CH3OH(g)
H = cH (CO) + 2 x cH (H2) - cH (CH3OH) +O2 +O2
cH(CO) + cH(CH3OH)
H = -283+ 2x –286 - -671 2x cH (H2)
CO2 (g) + 2 H2O (l)
= -184 kJ mol-1
Example 4. Using the following combustion data to calculate the heat of formation of propene
3C (s) + 3H2 (g)  C3H6 (g)
cH C (s) = -393kJ mol-1 cH H2 (g)= –286 kJ mol-1 cH C3H6(g)= –-2058 kJ mol-1
f H
H = Σ cH reactants - Σ cH products
3C (s) + 3H2 (g) C3H6 (g)
fH = 3 x cH (C) + 3 x cH (H2 ) - cH (C3H6)
3 x cH (C) + cH(C3H6)
fH = 3x -393+ 3x –286 - -2058 3 x cH (H2 )
= +21 kJ mol-1
3 CO2 (g) + 3 H2O (l)
Measuring the enthalpy change for a reaction experimentally
Calorimetric method This equation will only give the
energy for the actual quantities
used. Normally this value is
For a reaction in solution we use the following equation converted into the energy
energy change = mass of solution x heat capacity x temperature change change per mole of one of the
Q (J) = m (g) x cp (J g-1K-1) x T ( K) reactants. (The enthalpy
change of reaction, Hr)
Calorimetric method Practical
One type of experiment is one in which substances are This could be a solid dissolving or reacting
mixed in an insulated container and the temperature rise in a solution or it could be two solutions
measured. reacting together
General method
 washes the equipment (cup and pipettes etc) with the solutions to be used
 dry the cup after washing
 put polystyrene cup in a beaker for insulation and support
 Measure out desired volumes of solutions with volumetric pipettes and transfer to
insulated cup
 clamp thermometer into place making sure the thermometer bulb is immersed in solution
 measure the initial temperatures of the solution or both solutions if 2 are used. Do this
every minute for 2-3 minutes
 At minute 3 transfer second reagent to cup. If a solid reagent is used then add the
solution to the cup first and then add the solid weighed out on a balance.
 If using a solid reagent then use ‘before and after’ weighing method
 stirs mixture (ensures that all of the solution is at the same temperature)
 Record temperature every minute after addition for several minutes
If the reaction is slow then the exact temperature rise can be

difficult to obtain as cooling occurs simultaneously with the
reaction
To counteract this we take readings at regular time intervals

and extrapolate the temperature curve/line back to the time
the reactants were added together.
We also take the temperature of the reactants for a few

minutes before they are added together to get a better
average temperature. If the two reactants are solutions then
the temperature of both solutions need to be measured
before addition and an average temperature is used.
Errors in this method Read question

carefully. It may be
• energy transfer from surroundings (usually loss) necessary to describe:
• approximation in specific heat capacity of solution. The method assumes all • Method
solutions have the heat capacity of water. • Drawing of graph
• neglecting the specific heat capacity of the calorimeter- we ignore any with extrapolation
energy absorbed by the apparatus. • Description of the
• reaction or dissolving may be incomplete or slow. calculation
• Density of solution is taken to be the same as water.
Calculating the enthalpy change of reaction, Hr from experimental data
The heat capacity of water is
General method 4.18 J g-1K-1. In any reaction
where the reactants are
1. Using q= m x cp x T calculate energy change for quantities used dissolved in water we assume
that the heat capacity is the
2. Work out the moles of the reactants used same as pure water.
3. Divide q by the number of moles of the reactant not in excess to give H Also assume that the solutions
have the density of water,
4. Add a sign and unit (divide by a thousand to convert Jmol-1 to kJmol-1
which is 1g cm-3. Eg 25cm3 will
weigh 25 g
Example 5. Calculate the enthalpy change of reaction for the reaction where 25cm3 of 0.2 M
copper sulphate was reacted with 0.01mol (excess of zinc). The temperature increased 7oC .
Step 1: Calculate the energy change for the amount of reactants in the test tube.
Q = m x cp x T Note the mass is the mass of the copper sulphate
Q = 25 x 4.18 x 7 solution only. Do not include mass of zinc powder.
Q = 731.5 J
Step 2 : calculate the number of moles of the reactant not in excess.
moles of CuSO4 = conc x vol If you are not told what is in excess, then you need to
= 0.2 x 25/1000 work out the moles of both reactants and work out
= 0.005 mol using the balanced equation which one is in excess.
Step 3 : calculate the enthalpy change per mole which is often called H (the enthalpy change of reaction)
H = Q/ no of moles
= 731.5/0.005
= 146300 J mol-1
Remember in these
= 146 kJ mol-1 to 3 sf
questions: sign,
Finally add in the sign to represent the energy change: if temp increases unit, 3 sig figs.
the reaction is exothermic and is given a minus sign e.g. –146 kJ mol-1
Example 6. 25cm3 of 2M HCl was neutralised by 25cm3 of 2M NaOH. The Temperature increased 13.5oC
What was the energy change per mole of HCl?
Step 1: Calculate the energy change for the amount of reactants in the test tube.
Q = m x cp x T Note the mass equals the mass of acid + the
Q = 50 x 4.18 x13.5 mass of alkali, as they are both solutions.
Q = 2821.5 J
Step 2 : calculate the number of moles of the HCl.
moles of HCl = conc x vol

= 2 x 25/1000
= 0. 05 mol
Step 3 : calculate H, the enthalpy change per mole which might be called the enthalpy change of neutralisation
Hr = Q/ no of moles
= 2821.5/0.05
= 564300 J mol-1
Remember in these
Exothermic and so is given a minus sign questions: sign,
= -56.4 kJ mol-1 to 3 sf
unit, 3 sig figs.
6
Measuring Enthalpies of combustion using calorimetry
Enthalpies of combustion can be calculated by using calorimetry. Generally the fuel is burnt and the flame
is used to heat up water in a metal cup
Example 7. Calculate the enthalpy change of combustion for the reaction where 0.65g of propan-1-ol was
completely combusted and used to heat up 150g of water from 20.1 to 45.5oC
Step 1: Calculate the energy change used to heat up the water.
Q = m x cp x T
Note the mass is the mass of water in the
Q = 150 x 4.18 x 25.4 calorimeter and not the alcohol
Q = 15925.8 J
Step 2 : calculate the number of moles of alcohol combusted.
moles of propan-1-ol = mass/ Mr

= 0.65 / 60
= 0.01083 mol
Step 3 : calculate the enthalpy change per mole which is called Hc (the enthalpy change of combustion)
H = Q/ no of moles
= 15925.8/0.01083
= 1470073 J mol-1
Remember in these
= 1470 kJ mol-1 to 3 sf
questions: sign,
Finally add in the sign to represent the energy change: if temp increases unit, 3 sig figs.
the reaction is exothermic and is given a minus sign eg –1470 kJ mol-1
Errors in this method
• Energy losses from calorimeter

• Incomplete combustion of fuel
• Incomplete transfer of energy
• Evaporation of fuel after weighing
• Heat capacity of calorimeter not included
• Measurements not carried out under standard conditions as
H2O is gas, not liquid, in this experiment
Mean Bond enthalpies
These values are positive because
Definition: The Mean bond enthalpy is the enthalpy needed to
energy is required to break a bond.
break the covalent bond into gaseous atoms, averaged over
different molecules
The definition only applies when the
substances start and end in the
We use values of mean bond enthalpies because every single
gaseous state.
bond in a compound has a slightly different bond energy. E.g. In
CH4 there are 4 C-H bonds. Breaking each one will require a
different amount of energy. However, we use an average value for
the C-H bond for all hydrocarbons.
The value for the bond enthalpy for the C-H bond in methane matches this reaction ¼ CH4 (g)  C (g) + H (g)
Gaseous atoms
Gaseous atoms
Energy
Energy
Energy
Energy
breaking Activation In an exothermic reaction Energy
breaking Activation making
bonds Energy Energy the sum of the bonds in Energy
bonds products bonds
reactants making
bonds
the reactant molecules
H will be less than the sum H
products reactants
of the bonds in the
product molecules
Progress of reaction
Progress of reaction
Reaction profile for an Reaction profile for an
EXOTHERMIC reaction ENDOTHERMIC reaction
In general (if all substances are gases)

H =  bond enthalpies broken -  bond enthalpies made
H reaction
Reactants Products
Σbond energies Σbond energies

broken in reactants made in products
Gaseous atoms of
elements
H values calculated using this method will be less accuate

than using formation or combustion data because the mean
bond energies are not exact
Example 8. Using the following mean bond enthalpy data to calculate Bond Mean enthalpy
the heat of combustion of propene
(kJ mol-1)
H H
O C=C 612
H C C C + 4.5 O O 3 O C O + 3
H H C-C 348
H H
H
O=O 496
= [E(C=C) + E(C-C) + 6 x E(C-H) + 4.5 x E(O=O)] – [ 6 xE(C=O) + 6 E(O-H)] O=C 743
= [ 612 + 348 + (6 x 412) + (4.5 x 496) ] – [ (6 x 743) + (6 X 463)] O-H 463
= - 1572 kJmol-1 C-H 412
Example 9. Using the following mean bond enthalpy data to calculate the heat of formation of NH3
½ N2 + 1.5 H2  NH3 (note the balancing is to agree with the definition of heat of formation (i.e. one mole of product)
E(N≡N) = 944 kJ mol-1 E(H-H) = 436 kJ mol-1 E(N-H) = 388 kJ mol-1

= [0.5 x E(N≡N) + 1.5 x E(H-H)] – [ 3 xE(N-H)]

= [ (0.5 x 944) + (1.5 x 436) ] – [ 3 x 388)]
= - 38 kJmol-1
A more complicated example that may occur at AS

This is a more complicated
Working out Hf of a compound using bond energies and other data example of the type in example 9
elements Hf
Compound in
standard state The H’s can be
combinations of
H to turn elements H to turn
compound into different data
into gaseous atoms
gaseous atoms
Gaseous atoms
Can be bond energies

E(Cl-Cl) Cl2  2Cl  bond energies of
Or atomisation energies (if compound + (H to turn to
the substance is not diatomic gas if compound is not
gaseous)
C(s)  C(g)
Example 10
Calculate ΔHf for propane, C3H8(g), given the following data. Bond C–C C–H H–H
C(s)  C(g) ΔH = 715 kJ mol-1
kJ mol-1 348 412 436
3C (s) + 4H2 (g)  C3H8(g),
Σ H to turn elements - Σ H to turn compound

Hf =
into gaseous atoms into gaseous atoms
 Hf = (3xHat [C] + 4 x E[H-H] ) – (2 x E[C-C]+ 8 x E[C-H] )

= (3x715 + 4 x 436 ) – (2 x 348+ 8 x 412 )
=-103 kJ mol-1
Enthalpies of combustion in a homologous series
When comparing the heats of combustion for successive members of a homologous series such as
alkanes or alcohols there is a constant rise in the size of the heats of combustion as the number of
carbon atoms increases
H H O 1 C-C, 5C-H 1C-O 1O-H and 3 O=O

H C C O H + 3 O O 2 O C O + 3
H H
bonds are broken
H H 4 C=O and 6 O-H bonds are made
ethanol ΔHc = -1365 kJ mol-1
H H H 2C-C, 7C-H 1C-O 1O-H and 4.5 O=O

O bonds are broken
H C C C O H + 4.5 O O 3 O C O + 4
H H 6 C=O and 8 O-H bonds are made
H H H
ΔHc = -2016 kJ mol-1
Propan-1-ol
H H H H
3C-C, 9C-H 1C-O 1O-H and 6 O=O
H C C C C O H + 6 O
4 bonds are broken
O O O C O+ 5 H H
H H H H
8 C=O and 10 O-H bonds are made
Butan-1-ol
ΔHc = -2677 kJ mol-1
As one goes up the homologous series there is a constant amount and type of extra bonds being broken and
made e.g. 1C-C, 2C-H and 1.5 O=O extra bonds broken and 2 C=O and 2 O-H extra bonds made, so the
enthalpy of combustion increases by a constant amount
calculated If the results are worked out experimentally

using a calorimeter the experimental results
kJ mol-1
combustion
Enthalpy of
will be much lower than the calculated ones

because there will be significant heat loss.
There will also be incomplete combustion
experimental which will lead to less energy being
released.
Mr of alcohol
Remember that calculated values of enthalpy of combustions will

be more accurate if calculated from enthalpy of formation data than
if calculated from average bond enthalpies. This is because
average bond enthalpy values are averaged values of the bond
enthalpies from various compounds.
9. Kinetics I
Collision theory
Energy
Reactions can only occur when collisions take place Activation
between particles having sufficient energy. The energy is Energy:
usually needed to break the relevant bonds in one or EA
either of the reactant molecules. reactants
This minimum energy is called the Activation Energy
∆H
The Activation Energy is defined as the minimum
products
energy which particles need to collide to start a reaction
Maxwell Boltzmann Distribution Progress of Reaction

The Maxwell-Boltzmann energy distribution shows the spread of energies that
Learn this curve
molecules of a gas or liquid have at a particular temperature
carefully
Emp this is the most

probable energy (not the
same as mean energy) The area under the curve
represents the total number of
A few have low particles present
energies because
collisions cause some
Fraction of molecules
Most molecules have energies

particles to slow down between the two extremes but the
distribution is not symmetrical (normal)
with energy
Only a few particles

have energy greater
than the EA
Emp Collision energy
Ea
The energy distribution

The mean energy of The energy distribution should
should go through the
the particles is not at never meet the x axis, as there is
origin because there are
the peak of the curve no maximum energy for molecules
no molecules with no
energy
Q. How can a reaction go to completion if few particles have energy greater than Ea?
A. Particles can gain energy through collisions
Increasing Temperature As the temperature increases the distribution shifts

towards having more molecules with higher energies
At higher temps both the Emp and mean energy shift to high energy
Lower temperature
values although the number of molecules with those energies decrease
T= 25OC
with energy
higher temperature
T= 1067OC
with energy
mean
Collision energy
Ea
Collision energy
The total area under the curve should remain constant
because the total number of particles is constant At higher temperatures the molecules have a wider
range of energies than at lower temperatures.
1
Measuring Reaction Rates
The rate of reaction is defined as the change in concentration of a substance in unit time
Its usual unit is mol dm-3s-1
When a graph of concentration of reactant is plotted vs Initial rate =

time, the gradient of the curve is the rate of reaction. gradient of
concentration
tangent
The initial rate is the rate at the start of the
reaction where it is fastest
Reaction rates can be calculated from graphs of

concentration of reactants or products
time
In the experiment between sodium thiosulphate and hydrochloric acid we usually measure reaction rate as
1/time where the time is the time taken for a cross placed underneath the reaction mixture to disappear due
to the cloudiness of the Sulphur . Na2S2O3 + 2HCl 2NaCl + SO2 + S + H2O
This is an approximation for rate of reaction as it does not include concentration. We can use this because
we can assume the amount of Sulphur produced is fixed and constant.
Effect of Increasing Concentration and Increasing Pressure
At higher concentrations(and pressures) there are more particles per

unit volume and so the particles collide with a greater frequency
and there will be a higher frequency of effective collisions.
Note: If a question mentions a doubling of concentration/rate

then make sure you mention double the number of particles Higher concentration
Number of molecules
per unit volume and double the frequency of effective

collisions.
lower concentration
If concentration increases, the shape of the energy distribution
with energy
curves do not change (i.e. the peak is at the same energy) so

the Emp and mean energy do not change
They curves will be higher, and the area under the curves will
be greater because there are more particles
Collision energy
Ea
More molecules have energy > EA (although not a greater proportion)
Comparing rate curves

Need to calculate/ compare
Amount of initial moles of reactants to
product e.g. A
distinguish between different
Volume of B finishing volumes.
gas
e.g. the amount of product is
Different volumes of the C proportional to the moles of
D
same initial concentrations reactant
will have the same initial
rate (if other conditions are Time (secs)
the same) but will end at The higher the concentration/ temperature/
different amounts surface area the faster the rate (steeper the
gradient)
Effect of Increasing Temperature
At higher temperatures the energy of the particles Lower temperature
increases. They collide more frequently and more
often with energy greater than the activation energy.
with energy
More collisions result in a reaction
higher temperature
As the temperature increases, the graph shows
that a significantly bigger proportion of particles
have energy greater than the activation energy,
so the frequency of successful collisions
increases Collision energy
Ea
Effect of Increasing Surface area

Increasing surface area will cause successful collisions to occur more frequently between the
reactant particles and this increases the rate of the reaction.
Effect of Catalysts
Definition: Catalysts increase reaction rates without getting used up.
Explanation: They do this by providing an alternative route or mechanism with a lower

activation energy
Activation
Energy:
Comparison of the activation energies for an uncatalysed
uncatalysed reaction and for the same reaction with
a catalyst present. reactants EA catalysed
∆H
products
Progress of Reaction
If the activation energy is lower, more

particles will have energy > EA, so
there will be a higher frequency of With a lower activation
effective collisions. The reaction will be energy more particles have
faster energy greater than the

activation energy
with energy
Collision energy
Ea un catalysed
catalysed Ea
Heterogeneous catalysis
Adsorption of reactants at active sites on the surface
A heterogeneous catalyst is in a different may lead to catalytic action. The active site is the place
phase from the reactants where the reactants adsorb on to the surface of the
catalyst. This can result in the bonds within the reactant
molecules becoming weaker, or the molecules being held in
Heterogeneous catalysts are usually solids
a more reactive configuration. There will also be a higher
whereas the reactants are gaseous or in solution. concentration of reactants at the solid surface so leading to
The reaction occurs at the surface of the catalyst. a higher collision frequency
Effect of pressure on heterogenous Catalysis.
Increasing pressure has limited effect on the rate of heterogenous catalysed reactions because the reaction
takes place on surface of the catalyst. The active sites on the catalyst surface are already saturated with
reactant molecules so increasing pressure wont have an effect
Industrially catalysts speeds up the

rate allowing lower temp to be used
(and hence lower energy costs) but
have no effect on equilibrium
Environmental benefits of Catalysts

Catalysed reactions can occur at lower temperature so less fuel needed and fewer emissions from
fuels.
Catalysed reaction enables use of an alternative process with higher atom economy so meaning
fewer raw materials needed and less waste products are produced
10. Equilibrium I
Many reactions are reversible All reversible reactions reach an
N2 + 3H2 2NH3 dynamic equilibrium state.
We use the expression ‘position of

Dynamic equilibrium occurs when forward and
equilibrium’ to describe the composition of the
backward reactions are occurring at equal rates. The
equilibrium mixture.
concentrations of reactants and products stays
constant and the reaction is continuous.
If the position of equilibrium favours the
reactants (also described as “towards the left”)
then the equilibrium mixture will contain mostly
reactants.
Le Chatelier’s Principle
We use Le Chatelier’s principle to work out how Le Chatelier’s principle states that if an external
changing external conditions such as temperature condition is changed the equilibrium will shift to
and pressure affect the position of equilibrium oppose the change (and try to reverse it).
Effect of Temperature on equilibrium

Typical Exam question: What effect would increasing
If temperature is increased the equilibrium will
temperature have on the yield of ammonia?
shift to oppose this and move in the
endothermic direction to try and reduce the N2 + 3H2 2NH3 H = -ve exo
temperature by absorbing heat.
Exam level answer : must include bold points
And its reverse
If temperature is increased the equilibrium will
shift to oppose this and move in the endothermic,
If temperature is decreased the equilibrium
backwards direction to try to decrease
will shift to oppose this and move in the
temperature. The position of equilibrium will shift
exothermic direction to try and increase the
towards the left, giving a lower yield of ammonia.
temperature by giving out heat.
Low temperatures may give a higher yield of product but will also result in slow rates of
reaction. Often a compromise temperature is used that gives a reasonable yield and rate
Effect of Pressure on equilibrium

Typical Exam question: What effect would increasing
Increasing pressure will cause the equilibrium to shift
pressure have on the yield of methanol?
towards the side with fewer moles of gas to oppose
the change and thereby reduce the pressure. CO (g) + 2H2(g) CH3OH (g)
And its reverse

Exam level answer : must include bold points
If pressure is increased the equilibrium will shift
Decreasing pressure will cause the equilibrium to shift to oppose this and move towards the side with
towards the side with more moles of gas to oppose fewer moles of gas to try to reduce the
the change and thereby increase the pressure. pressure . The position of equilibrium will shift
towards the right because there are 3 moles of
If the number of moles of gas is the same on both gas on the left but only 1 mole of gas on the right,
sides of the equation then changing pressure will have giving a higher yield of methanol.
no effect on the position of equilibrium
H2 + Cl2 2HCl
Increasing pressure may give a higher yield of product and will produce a faster rate. Industrially high
pressures are expensive to produce ( high electrical energy costs for pumping the gases to make
a high pressure) and the equipment is expensive (to contain the high pressures)
Effect of Concentration on equilibrium
Increasing the concentration OH- ions causes the equilibrium to shift to
I2 + 2OH- I- + IO- + H2O oppose this and move in the forward direction to remove OH- ions. The
position of equilibrium will shift towards the right, giving a higher yield
brown colourless
of I- and IO-. ( The colour would change from brown to colourless)
Adding H+ ions reacts with the OH- ions and reduces their concentration
so the equilibrium shifts back to the left giving brown colour.
Effect of Catalysts on equilibrium

A catalyst has no effect on the position of equilibrium, but it will speed up the rate at which the
equilibrium is achieved.
It does not effect the position of equilibrium because it speeds up the rates of the forward and
backward reactions by the same amount.
Importance of equilibrium to industrial processes
You should be able to apply the above ideas to given reactions

Common examples
Contact process
Haber process
Stage 1 S (s) + O2 (g)  SO2 (g)
N2 + 3H2 2NH3 H = -ve exo
Stage 2 SO2 (g) + ½ O2 (g) SO3 (g) H = -98 kJ mol-1
T= 450oC, P= 200 – 1000 atm, catalyst = iron
T= 450oC, P= 1 to 2 atm, catalyst = V2O5
Low temp gives good yield but slow rate:
Low temp gives good yield but slow rate: compromise
compromise temp used
moderate temp used
High pressure gives good yield and high rate:
High pressure gives slightly better yield and high rate: too
too high a pressure would lead to too high
high a pressure would lead to too high energy costs for
energy costs for pumps to produce the pressure
pumps to produce the pressure
Hydration of ethene to produce ethanol

Production of methanol from CO
CH2=CH2 (g) + H2O (g) CH3CH2OH(l) H = -ve
CO (g) + 2H2(g) CH3OH (g) H = -ve exo
T= 300oC, P= 70 atm, catalyst = conc H3PO4
T= 400oC, P= 50 atm, catalyst = chromium and
zinc oxides Low temp gives good yield but slow rate: compromise
temp used
compromise temp used High pressure gives good yield and high rate: too high a
pressure would lead to too high energy costs for pumps
to produce the pressure
energy costs for pumps to produce the pressure High pressure also leads to unwanted polymerisation of
ethene to poly(ethene)
In all cases catalysts speeds up the rate allowing lower temp to be used (and hence lower energy costs)
but have no effect on equilibrium
In all cases high pressure leads to too high energy costs for pumps to produce the pressure and
too high equipment costs to have equipment that can withstand high pressures.
Recycling unreacted reactants back into the reactor can improve the overall yields of all these processes
2
Equilibrium constant Kc Kc = equilibrium constant
Example 1
For a generalised reaction
mA + nB pC + qD [ C]p [D]q N2 (g) + 3H2 (g) 2 NH3 (g)
Kc=
m,n,p,q are the stoichiometric balancing [ A]m [B]n
numbers [NH3 (g)]2
Kc=
A,B,C,D stand for the chemical formula [N2 (g)] [H2 (g)]3
[ ] means the equilibrium concentration
Calculating Kc
Example
H2 (g) +Cl2 (g) 2HCl (g)
For the following equilibrium
In a container of volume 600cm 3 at equilibrium the concentrations of the substances were 0.67 mol dm-3 of H2 and
0.83 mol dm-3 of Cl2 and 0.33 mol dm-3 HCl. Calculate Kc
[HCl (g)]2
Kc=
[H2 (g) ] [Cl2 (g)]
Kc
= 0.332 = 0.196 no unit
0.67x0.83
Effect of changing conditions on value of Kc

Kc only changes with temperature.
The larger the Kc the greater the amount of products. It does not change if pressure or
If Kc is small we say the equilibrium favours the reactants concentration is altered.
A catalyst also has no effect on Kc
11. Equilibrium II
Many reactions are reversible All reversible reactions reach an
N2 + 3H2 2NH3 dynamic equilibrium state.
Dynamic equilibrium occurs when forward and backward reactions are occurring at equal rates. The
concentrations of reactants and products stays constant and the reaction is continuous.
Writing an expression for Equilibrium constant Kc
Kc = equilibrium constant
For a generalised reaction Example 1
mA + nB pC + qD
[ C]p [D]q N2 (g) + 3H2 (g) 2 NH3 (g)
m,n,p,q are the stoichiometric balancing Kc=
numbers [ A]m [B]n [NH3 (g)]2
Kc=
A,B,C,D stand for the chemical formula
[N2 (g)] [H2 (g)]3
[ ] means the equilibrium concentration
The unit of Kc changes and depends on the equation.
Working out the unit of Kc
Put the unit of concentration (mol dm-3) into the Kc equation

Cancel out
[NH3 (g)]2 units 1
Kc= [mol dm-3]2 Unit = [mol dm-3]-2
Unit = Unit =
[N2 (g) ] [H2 (g)]3 [mol dm-3]2
[mol dm-3] [mol dm-3]3
Unit = mol-2 dm+6
Example 2: writing Kc expression

Working out the unit
H2 (g) +Cl2 (g) 2HCl (g) [HCl (g)]2
Kc= [mol dm-3]2
Unit Kc= = no unit
[H2 (g) ] [Cl2 (g)]
[mol dm-3] [mol dm-3]
Calculating Kc
Most questions first involve having to work out the equilibrium moles and then concentrations
of the reactants and products.
Usually the question will give the initial amounts (moles) of the reactants, and some data that
will help you work out the equilibrium amounts.
Calculating the moles at equilibrium
moles of reactant at equilibrium = initial moles – moles reacted
moles of product at equilibrium = initial moles + moles formed
Example 3
H2 (g) +Cl2 (g) 2HCl (g)
In a container of volume 600cm 3 there were initially 0.5mol of H2 and 0.6 mol of Cl2.
At equilibrium there were 0.2 moles of HCl. Calculate Kc
H2 Cl2 HCl
It is often useful Using the balanced equation if 0.2 moles of
Initial moles 0.5 0.6 0
to put the mole HCl has been formed it must have used up
data in a table. 0.1 of Cl2 and 0.1 moles of H2 (as 1:2 ratio)
Equilibrium moles 0.2
Work out the moles at equilibrium for the reactants moles of reactant at equilibrium = initial moles – moles reacted
moles of hydrogen at equilibrium = 0.5 – 0.1 = 0.4 moles of chlorine at equilibrium = 0.6 – 0.1 = 0.5
H2 Cl2 HCl If the Kc has no unit then there are equal numbers of
reactants and products. In this case you do not have to
Initial moles 0.5 0.6 0 divide by volume to work out concentration and equilibrium
moles could be put straight into the kc expression
Equilibrium moles 0.4 0.5 0.2
Equilibrium 0.4/0.6 0.5/0.6 0.2/0.6

[HCl (g)]2
concentration (M) =0.67 =0.83 =0.33 Kc=
[H2 (g) ] [Cl2 (g)]
Work out the

Finally put
Kc
= 0.332 = 0.196 no unit
concentrations into 0.67x0.83
equilibrium
conc = moles/ vol (in dm3) Kc expression
concentrations
Example 4
N2 (g) + 3H2 (g ) 2 NH3 (g)
Initially there were 1.5 moles of N2 and 4 mole of H2, in a 1.5 dm3 container. At
equilibrium 30% of the Nitrogen had reacted. Calculate Kc
N2 H2 NH3
30% of the nitrogen had reacted = 0.3 x1.5 = 0.45 moles reacted.
Initial moles 1.5 4.0 0 Using the balanced equation 3 x 0.45 moles of H 2 must have
reacted and 2x 0.45 moles of NH3 must have formed
Equilibrium moles
Work out the moles at equilibrium for the reactants and products
moles of nitrogen at equilibrium = 1.5 – 0.45 = 1.05 moles of hydrogen at equilibrium =4.0 – 0.45 x3 = 2.65
moles of ammonia at equilibrium = 0 + (0.45 x 2) = 0.9
N2 H2 NH3
Finally put concentrations into Kc expression
Equilibrium moles 1.05 2.65 0.9 [NH3 (g)]2

Kc=
Equilibrium 1.05/1.5 2.65/1.5 0.9/1.5 [N2 (g) ] [H2 (g)]3
concentration (M) =0.7 =1.77 =0.6
Kc
= 0.62 = 0.0927 mol-2 dm+6
Work out the 0.7x1.773
equilibrium
conc = moles/ vol (in dm3)
concentrations
Practical: Working out equilibrium constant Kc
A common experiment is working out the equilibrium constant for an esterification reaction. Ethanol and
ethanoic acid are mixed together with a sulphuric acid catalyst.
CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O

Ethanoic acid Ethanol Ethyl Ethanoate
Method
Part 1 Preparing the equilibrium mixture
1 Use burettes to prepare a mixture in boiling tube of carboxylic acid, alcohol, and dilute sulfuric acid.
2 Swirl and bung tube. Leave the mixture to reach equilibrium for one week
Part 2 Titrating the equilibrium mixture

1 Rinse a 250 cm3 volumetric flask with distilled water.
Use a funnel to transfer the contents of the boiling tube into the flask. Rinse the boiling tube with water and
add the washings to the volumetric flask.
2 Use distilled water to make up the solution in the volumetric flask to exactly 250 cm3.
Stopper the flask, then invert and shake the contents thoroughly.
3 Use the pipette to transfer 25.0 cm3 of the diluted equilibrium mixture to a 250 cm3 conical flask.
4 Add 3 or 4 drops of phenolphthalein indicator to the conical flask.
5 Set up the burette with sodium hydroxide solution..
6 Add the sodium hydroxide solution from the burette until the mixture in the conical flask just turns pink.
Record this burette reading in your table.
7 Repeat the titration until you obtain a minimum of two concordant titres.
The sodium hydroxide will react with the sulphuric acid catalyst and any unreacted carboxylic
acid in the equilibrium mixture
There are many different calculations that can be based on this experiment.
Let’s look at general stages. Not all calculations will use all the stages.
Working out initial amount of moles of reactants

The amount of moles of alcohol and carboxylic acid can be calculated from the
densities and volumes of liquids added
Mass = density x volume
then
Moles = mass X Mr
The initial amount of moles of acid catalyst used is usually determined by titrating a
separate sample of catalyst with sodium hydroxide
Working out equilibrium amount of moles of acid present from the titre results
39.0 cm3 of 0.400 mol dm-3 sodium hydroxide was used in the above titration. The initial moles of sulphuric acid
was 5x10-4 mol. Calculate the moles of ethanoic acid present at equilibrium
Amount of NaOH = vol X conc

= 0.039 x 0.400
= 0.0156 mol
So total amount of H+ present in 25cm3 = 0.0156 mol
So total amount of H+ present in 250cm3 = 0.156 mol
Total mol acid present = moles of carboxylic acid + moles of acid catalyst
So X 2 because H2SO4
Amount of carboxylic acid at equilibrium = 0.156 – (5x10-4 x 2) has 2 H+
= 0.155 mol
The pink colour of the phenolphthalein in the titration can fade after the end-point of the titration has
been reached because the addition of sodium hydroxide may make the equilibrium shift towards the
reactants
Working out equilibrium amount of moles of other substances
Calculate the equilibrium amount of ethanol, ethyl ethanoate and water if there were initially 0.400 mol of
ethanol and 0.500 mol of ethanoic acid and at equilibrium there were 0.155 mol of ethanoic acid.
Amount of ethanoic acid that reacted = initial amount – equilibrium amount

= 0.5 – 0.155
= 0.344mol
Amount of ethanol at equilibrium = initial amount - amount that reacted
= 0.400 – 0.344
= 0.056 mol
Amount of ethyl ethanoate at equilibrium = initial amount + amount that formed
= 0 + 0.344
= 0.344 mol
Amount of water at equilibrium = initial amount + amount that formed The amount of water at
= 0 + 0.344 equilibrium would not really be
= 0.344 mol 0 as there would be water
present in the acid catalyst
Calculating the equilibrium constant

Finally calculate the equilibrium constant.
To work out equilibrium concentrations divide the equilibrium amounts by the total volume. Then put in
Kc expression
Kc = [CH3CO2CH2CH3 ] [H2O]
[CH3CO2H] [CH3CH2OH]
In order to confirm that one week was sufficient time for

equilibrium to be established in the mixture from Part 1,
several mixtures could be made and left for different
amount of time. If the resulting Kc is the same value then
it can be concluded the time is sufficient
Partial Pressures and Kp
If a reaction contains gases an alternative equilibrium expression can be

set up using the partial pressures of the gases instead of concentrations
Partial Pressure
The partial pressure of a gas in a mixture is the pressure

that the gas would have if it alone occupied the volume partial pressure = mole fraction x total pressure
occupied by the whole mixture. of gas 1 of gas 1
If a mixture of gases contains 3 different gases then the p1 = x1 P

total pressure will equal the 3 partial pressure added
together
P =p1 + p2 + p3
mole fraction
mole fraction = number of moles of a gas
total number of moles of all gases
For a 3 part mixture

x1 = y1
y1+y2 +y3
Example : A mixture contains 0.2 moles N2, 0.5 moles O2 and 1.2 moles of CO2. If the total pressure is 3atm.
What are the partial pressures of the 3 gases?
Total moles of gas = 0.5 + 1.2+ 0.2

= 1.9
mole fraction = 0.2/1.9 mole fraction = 0.5/1.9 mole fraction = 1.2/1.9

of N2 =0.105 of O2 =0.263 of CO2 =0.632
Partial pressure =0.105x 3 Partial pressure = 0.263 x 3 Partial pressure = 0.632 x 3

of N2 =0.315 of O2 =0.789 of CO2 =1.896
Writing an expression for Kp
N2 (g) + 3H2 (g) 2 NH3 (g) p means the partial pressure of that gas
p 2 NH3 Kp = equilibrium constant

Kp=
p N2 p 3 H2 Only include gases in the Kp expression. Ignore
solids, liquids, and aqueous substances.
Working out the unit of Kp
Put the unit of pressure(atm) into the Kp equation
atm2
Unit = However, if the equation is
p 2 NH
Kp= 3 (g) atm atm3 written the other way round, the
pN2 (g) p 3H2 (g) value of Kp will be the inverse of
1 above and the units will be atm2.
Cancel out units Unit =
It is important therefore to write
atm2
an equation when quoting
Unit = atm-2 values of Kp.
Example 4
N2 (g) + 3H2 (g ) 2 NH3 (g)
1 mole of N2 and 3 moles of H2 are added together and the mixture is allowed to reach equilibrium. At
equilibrium 20% of the N2 has reacted. If the total pressure is 2atm what is the value of Kp?
N2 H2 NH3
20% of the nitrogen had reacted = 0.2 x1.0 = 0.2 moles reacted.
Initial moles 1.0 3.0 0 Using the balanced equation 3 x 0.2 moles of H2 must have
reacted and 2x 0.2 moles of NH3 must have formed
Equilibrium moles
Work out the moles at equilibrium for the reactants and products
moles of nitrogen at equilibrium = 1.0 – 0.2 = 0.8 moles of hydrogen at equilibrium =3.0 – 0.20 x3 = 2.40
moles of ammonia at equilibrium = 0 + (0.2 x 2) = 0.4
N2 H2 NH3
Finally put concentrations into Kp expression
Equilibrium moles 0.80 2.40 0.40 p 2 NH3 (g)

Kp=
Mole fractions 0.8/3.6 2.40/3.6 0.40/3.6 pN2 (g) p 3H2 (g)
=0.222 =0.667 =0.111
Partial pressure 0.222 0.667 x2 0.111 x2

Kc
= 0.2222 = 0.0469 atm-2
x2 = =1.33 = 0.222 0.444x1.333
0.444
Heterogeneous equilibria for Kp
Kp expressions only contain gaseous substances. Any substance with another state is left out
CaCO3 (s) CaO (s) + CO2 (g)
Kp =p CO2
Unit atm
Equilibrium constants and feasibility

Values of equilibrium constants can all be used to predict the extent a reaction might occur.
Reaction Reactants equal amounts Products Reaction goes
‘does not predominate in of products and predominate in to completion
go’ an equilibrium reactants an equilibrium
Kc < 10-10 Kc  0.1 Kc = 1 Kc 10 Kc > 1010
ΔStotal increases the magnitude of the equilibrium constant increases since ΔS = R lnK
Where K is equilibrium constant Kc or Kp
This equation shows a reaction with a Kc >1 will therefore have a positive ΔStotal
Application of rates and equilibrium
Effect of changing conditions on value of Kc or Kp Kc and Kp only change with
temperature.
The larger the Kc the greater the amount of products.
It does not change if pressure or
If Kc is small we say the equilibrium favours the reactants
concentration is altered.
A catalyst also has no effect on Kc or Kp
Effect of Temperature on position of equilibrium and Kc
In this equilibrium which is exothermic in the forward direction

Both the position of equilibrium
and the value of Kc or Kp will N2 (g) + 3H2 (g ) 2 NH3 (g)
change it temperature is altered
If temperature is increased the reaction will shift to oppose the change and
move in the backwards endothermic direction. The position of equilibrium
shifts left. The value of Kc gets smaller as there are fewer products.
Effect of Temperature on rate
As the temperature increases a significantly bigger proportion of particles have energy greater than the
activation energy, so the frequency of successful collisions increases
Effect of Concentration on position of equilibrium and Kc
Changing concentration would H2 (g) +Cl2 (g) 2HCl (g)

shift the position of
equilibrium but the value of
Kc would not change. Increasing concentration of H2 would move equilibrium to
the right lowering concentration of H2 and Cl2 and
increasing concentration of HCl. The new concentrations
would restore the equilibrium to the same value of Kc
Effect of Concentration and pressure on rate

At higher concentrations(and pressures) there are more particles per unit volume and so the particles
collide with a greater frequency and there will be a higher frequency of effective collisions.
Effect of Pressure on position of equilibrium and Kp
In this equilibrium which has fewer moles of gas on the product side
The position of equilibrium will
change it pressure is altered N2 (g) + 3H2 (g ) 2 NH3 (g)
but the value of Kp stays If pressure is increased the reaction will shift to oppose the change
constant as Kp only varies with and move in the forward direction to the side with fewer moles of gas.
temperature The position of equilibrium shifts right. The value of Kp stays the
same though as only temperature changes the value of Kp.
Increasing pressure does not change Kp.

The increased pressure increases the pressure terms p 2 NH3
Kp=
on bottom of Kp expression more than the top. The p N2 p 3 H2
system is now no longer in equilibrium so the
equilibrium shifts to the right increasing mole fractions x 2 NH3 . P2 Where P is total
of products and decreases the mole fractions of Kp=
x N2.P x3 H 3 pressure and x
reactants. The top of Kp expression therefore 2.P
mole fraction
increases and the bottom decreases until the original
value of Kp is restored x 2 NH3 . P2
Kp=
x N2 x3 H2. P4
7
Effect of catalysts on position of equilibrium and Kc
A catalyst has no effect on the position of equilibrium or values of Kc and Kp, but it will speed
up the rate at which the equilibrium is achieved.
It does not effect the position of equilibrium because it speeds up the rates of the forward and
backward reactions by the same amount.
Catalysts speeds up the rate allowing lower temperatures to be used (and hence lower energy costs) but
have no effect on equilibrium.
Importance of equilibrium to industrial processes
Common examples
Contact process
Haber process
Stage 1 S (s) + O2 (g)  SO2 (g)
N2 + 3H2 2NH3 H = -ve exo
Stage 2 SO2 (g) + ½ O2 (g) SO3 (g) H = -98 kJ mol-1
T= 450oC, P= 200 – 1000 atm, catalyst = iron
T= 450oC, P= 1 to 2 atm, catalyst = V2O5
Low temp gives good yield but slow rate: compromise
compromise temp used
moderate temp used
High pressure gives slightly better yield and high rate: too
high a pressure would lead to too high energy costs for
energy costs for pumps to produce the pressure
pumps to produce the pressure
In all cases high pressure leads to too high energy costs for pumps to produce the pressure and
too high equipment costs to have equipment that can withstand high pressures.
Recycling unreacted reactants back into the reactor can improve the overall yields of all these processes and
improve their atom economy
Industrial processes cannot be in equilibrium since the products are removed as they are formed
to improve conversion of reactants. They are not closed systems
12. Acid Base Equilibria
Bronsted-Lowry Definition of acid Base behaviour
A Bronsted-Lowry acid is defined as a substance that can donate a proton.

A Bronsted-Lowry base is defined as a substance that can accept a proton.
HCl (g) + H2O (l)  H3O+ (aq) + Cl- (aq)

Each acid is linked to a conjugate base on
acid base acid base the other side of the equation.
HNO3 + HNO2 ⇌ NO3– + H2NO2+ HCOOH + CH3(CH2)2COOH ⇌ HCOO– + CH3(CH2)2COOH2+

Acid 1 Base 2 Base 1 Acid 2 Acid 1 Base 2 Base 1 Acid 2
In these reactions the substance with bigger Ka will act as

the acid
Calculating pH
pH = - log [H+] Where [H+] is the concentration of hydrogen ions in the solution
Calculating pH of strong acids

The concentration of hydrogen ions in a monoprotic strong acid
Strong acids completely dissociate
will be the same as the concentration of the acid.
For HCl and HNO3 the [H+(aq)] will be the same as the
original concentration of the acid. Always give pH values to 2d.p. In the exam
For 0.1M HCl the pH will be –log[0.1] =1.00
Finding [H+] from pH

On most calculators this is Example 1
[H+] = 1x 10-pH done by pressing What is the concentration of HCl with a pH of
Inv (or 2nd function) log 1.35?
 - number(pH) [H ] = 1 x 10-1.35 = 0.045M
+
Ionic Product for water

In all aqueous solutions and pure water the following equilibrium occurs: H2O (l) H+ (aq) + OH- (aq)
This equilibrium has the following Because [H2O (l)] is much bigger than the
equilibrium expression concentrations of the ions, we assume its
value is constant and make a new
Rearrange to constant Kw
[H+ ][OH- (aq)]
Kc= (aq) Kc x [H2O (l)] = [H+ (aq) ][OH- (aq)]
Kw = [H+ (aq) ][OH- (aq) ]
[H2O(l)]
Learn this expression
At 25oC the value of Kw for all aqueous solutions is 1x10-14 mol2dm-6 The Kw expression can be used to
calculate [H+ (aq)] ions if we know
pKw the [OH- (aq)] ions and vice versa.
Sometimes Kw is quoted as pKw values
pKw = -log Kw so Kw = 10-pKw
If Kw = 1x10-14 then pKw =14
Finding pH of pure water
Pure water/ neutral solutions are neutral because the [H+ (aq) ] = [OH-(aq)]
Using Kw = [H+ (aq) ][OH- (aq) ] then when neutral Kw = [H+ (aq) ]2
and [H+(aq) ] = √ Kw
At 25oC [H+(aq) ] = √ 1x10-14 = 1x10-7 so pH = 7
At different temperatures to 25oC the pH of

Example 2 : Calculate the pH of water at 50ºC given that Kw =
pure water changes. Le Chatelier’s
5.476 x 10-14 mol2 dm-6 at 50ºC
principle can predict the change. The
[H+(aq) ] = √ Kw = √ 5.476 x 10-14 =2.34 x 10-7 mol dm-3
dissociation of water is endothermic so
pH = - log 2.34 x 10-7 = 6.6
increasing the temperature would push the
It is still neutral though as [H+ (aq) ] = [OH- (aq)]
equilibrium to the right giving a bigger
concentration of H+ ions and a lower pH.
Calculating pH of Strong Base
For bases we are normally given the Example 3: What is the pH of the strong base 0.1M NaOH
concentration of the hydroxide ion.
Assume complete dissociation.
To work out the pH we need to work out [H+(aq)]
Kw = [H+ (aq)][OH- (aq)] = 1x10-14
using the kw expression.
[H+(aq)] = kw/ [OH- (aq)] = 1x10-14 / 0.1 = 1x10-13 M
Strong bases completely dissociate into their ions. pH = - log[1x10-13 ] =13.00
NaOH  Na+ + OH-
Weak acids
Weak acids only slightly dissociate when dissolved in water, giving an equilibrium mixture
We can simplify this to

HA + H2O (l) H3O+ (aq) + A- (aq) HA (aq) H+ (aq) + A- (aq)
Weak acids dissociation expression Example 4 Write an equation for dissociation of propanoic acid
and its ka expression
[H+ (aq)][A- (aq)]
Ka= CH3CH2CO2H(aq) H+ (aq) + CH3CH2CO2- (aq)
[HA (aq)]
[H+ (aq)][CH3CH2CO2-(aq)]
Ka=
The Ka for ethanoic acid is 1.7 x 10-5 mol [CH3CH2CO2H(aq)]
dm-3.
pKa
The larger ka the stronger the acid Sometimes Ka values are quoted as pKa values
pKa = -log Ka so Ka = 10-pKa
Calculating pH of a weak acid
To make the calculation easier two assumptions are made to [H+ (aq)][A- (aq)]
simplify the Ka expression: Ka=
[HA (aq)]
1) [H+ (aq)]eqm = [A- (aq)] eqm because they have dissociated
according to a 1:1 ratio. Simplifies to
2) As the amount of dissociation is small we assume that the initial [H+ (aq)]2
concentration of the undissociated acid has remained constant. Ka=
[HA (aq)]initial
So [HA (aq) ] eqm = [HA(aq) ] initial
Example 5 What is the pH of a solution of 0.01M ethanoic acid (ka is 1.7 x 10-5 mol dm-3)?
CH3CO2H(aq) H+ (aq) + CH3CO2- (aq)
[H+ (aq)]2 [H+ (aq)]2

[H+ (aq)][CH3CO2-(aq)]
Ka= Ka= 1.7x 10-5 =
[CH3CO2H(aq)]initial 0.01
[CH3CO2H(aq)]
[H+ (aq)]2 = 1.7 x 10-5 x 0.01 pH = - log [H+] = -log (4.12 x10-4)
pH =3.38
[H+ (aq)] = √ 1.7 x 10-7 = 4.12 x 10-4
Example 6 What is the concentration of propanoic acid with a pH of 3.52 (ka is 1.35 x 10-5 mol dm-3)?
CH3CH2CO2H(aq) H+ (aq) + CH3CH2CO2- (aq)
[H+] = 1 x 10-3.52 = 0.000302M

[H+ (aq)]2 [0.000302]2
[H+ (aq)][CH3CH2CO2-(aq)]
Ka= Ka= 1.35 x 10-5 =
[CH3CH2CO2H(aq)]initial [CH3CH2CO2H(aq)]initial
[CH3CH2CO2H(aq)]
[CH3CH2CO2H(aq)] = 9.12 x 10-8 /1.35 x 10-5 [CH3CH2CO2H(aq)] = 6.75 x 10-3 M
Working out pH of a weak acid at half equivalence

Example 7
When a weak acid has been reacted with exactly half the
What is the pH of the resulting solution when
neutralisation volume of alkali, the above calculation can be
25cm3 of 0.1M NaOH is added to 50cm3 of
simplified considerably.
0.1M CH3COOH (ka 1.7 x 10-5 )
ka = [H+] [CH3CO2- ] At half neutralisation we can make From the volumes and concentrations spot it
[ CH3CO2H ] the assumption that [HA] = [A-] is half neutralisation (or calculate)
So [H+(aq)] = ka pH = pka = -log (1.7 x 10-5 ) = 4.77

And pH = pka
Diluting an acid or alkali

pH of diluted base
pH of diluted strong acid [OH–] = [OH–]old x old volume
new volume
[H+] = [H+]old x old volume
[H+] = Kw
new volume [OH– ]
pH = – log [H+] pH = – log [H+]
Example 8 Calculate the new pH when 50.0 cm3 of 0.150 mol dm-3 HCl is mixed with 500 cm3 of water.
[H+(aq)] = 0.0136
[H+] = [H+]old x old volume 0.05
[H+(aq)] = 0.150 x
new volume 0.55 pH = – log [H+]
= -log 0.0136
= 1.87
Comparing the pH of a strong acid and a weak acid after dilution 10, 100 and 1000 times
Because pH is a logarithmic scale, diluting a strong acid 10 times will increase its pH
by one unit, and diluting it 100 times would increase its pH by two units
Weak acids would not change in the same way as when they are diluted. They increase by less than 1 unit
CH3CH2CO2H +H2O H3O+ + CH3CH2CO2-
Diluting the weak acid pushes the equilibrium to the right so the degree of dissociation increases and
more H+ ions are produced meaning pH increases less than expected
Buffer Solutions
A Buffer solution is one where the pH does not change
significantly if small amounts of acid or alkali are added to it. A basic buffer solution is made from a weak
base and a salt of that weak base ( made
An acidic buffer solution is made from a weak acid and a salt from reacting the weak base with a strong
of that weak acid ( made from reacting the weak acid with a acid).
strong base). Example :ammonia and ammonium chloride
Example : ethanoic acid and sodium ethanoate NH3 and NH4+Cl-
CH3CO2H (aq) and CH3CO2- Na+
How Buffer solutions work

In an ethanoic acid buffer
In a buffer solution there is a much
CH3CO2H (aq) CH3CO2- (aq) + H+ (aq) higher concentration of the salt
CH3CO2- ion than in the pure acid.
Acid conjugate base
The buffer contains a reservoir of HA and A — ions
If small amounts of acid is added to the buffer: Then the above equilibrium
will shift to the left removing nearly all the H+ ions added, CH3CO2- (aq) + H+ [CH3CO2H (aq)]
[H+(aq)] = Ka
(aq)  CH3CO2H (aq)
[CH3CO2-(aq) ]
As there is a large concentration of the salt ion in the buffer the ratio
[CH3CO2H]/ [CH3CO2-] stays almost constant, so the pH stays fairly
constant.
If small amounts of alkali is added to the buffer. The OH- ions will react with H+ ions to
form water.
Learn these
H+ + OH -  H2O explanations carefully
and be able to write
The Equilibrium will then shift to the right to produce more H+ ions. the equilibrium to
illustrate your
CH3CO2H (aq) CH3CO2- (aq) + H+ (aq)
answer.
Some ethanoic acid molecules are changed to ethanoate ions but as there is a large
concentration of the salt ion in the buffer the ratio [CH3CO2H]/ [CH3CO2-] stays almost
constant, so the pH stays fairly constant.
Calculating the pH of buffer solutions
We still use the weak acids dissociation expression
Normally we
[H+ (aq)][A- (aq)] But here we assume the [A-] [H+(aq)] = Ka
[HA(aq)]
Ka= rearrange to
concentration is due to the
[HA (aq)] [A- (aq) ]
added salt only
We also assume the Initial concentration of

the acid has remained constant, because
amount that has dissociated or reacted is
The salt content can be added in several ways: a salt solution
small.
could be added to the acid or some solid salt added. A buffer can
also be made by partially neutralising a weak acid with alkali and
therefore producing salt.
Example 9: making a buffer by adding a salt solution
We can enter moles of
What would be the pH of a buffer made from 45cm 3 of 0.1M ethanoic acid acid and salt straight
and 50cm3 of 0.15 M sodium ethanoate (Ka = 1.7 x 10 -5) ? into the equation as
they both have the
Work out the moles of both solutions same new final volume
Moles ethanoic = conc x vol = 0.1 x 0.045 = 0.0045mol [HA(aq)]
[H+(aq)] = Ka
Moles sodium ethanoate = conc x vol = 0.15 x 0.050 = 0.0075 [A- (aq) ]
0.0045
[H+(aq)] = 1.7 x 10-5 x [H+(aq)] = 1.02x 10-5 pH = – log [H+]
0.0075 = -log 1.02x 10-5
= 4.99
Example 10 : making a buffer by adding a solid salt

A buffer solution is made by adding 1.1g of sodium ethanoate into 100 cm 3 acid and salt straight
of 0.4M ethanoic acid. What is its pH? Ka =1.7 x10 -5 into the equation as
they both have the
Work out the moles of both solutions same new final volume
Moles ethanoic = conc x vol = 0.4 x 0.1 = 0.04mol [HA(aq)]
[H+(aq)] = Ka
Moles sodium ethanoate = mass/Mr= 1.1/82 = 0.0134 [A- (aq) ]
0.04
0.0134 = -log 5.07x 10-5
= 4.29
If a buffer is made by adding sodium hydroxide to partially neutralise a weak acid then follow the method below
Example 11 55cm3 of 0.5M CH3CO2H is reacted with 25cm3 of 0.35M NaOH. What will be the pH of the resulting buffer
solution?
CH3CO2H+ NaOH  CH3CO2Na + H2O
Moles CH3CO2H = conc x vol =0.5x 0.055 = 0.0275mol
ka is 1.7 x 10-5 mol dm-3
Moles NaOH = conc x vol = 0.35 x 0.025 = 0.00875
Moles of CH3CO2H in excess = 0.0275-0.00875 = 0.01875 (as 1:1 ratio)
[CH3CO2H ] = moles excess CH3CO2H [CH3CO2- ] = moles OH- added

total volume (dm3) total volume (dm3)
= 0.01875/ 0.08 = 0.234M = 0.00875/ 0.08 = 0.109M
ka = [H+] [CH3CO2- ]
[H+] = ka x[ CH3CO2H ] / [CH3CO2- ]
[ CH3CO2H ] pH = – log [H+]
= 1.7 x 10-5x 0.234 / 0.109 = -log 3.64 x 10-5
= 3.64 x 10-5 = 4.44
Buffering action in blood

Equilibrium
A carbonic acid– hydrogencarbonate equilibrium acts H2CO3 ⇌ H+ + HCO3 –
as a buffer in the control of blood pH
Adding alkali reacts with H+ so the above Equilibrium
The H2CO3/HCO3– buffer is present in would shift right forming new H+ and more HCO3 –
blood plasma, maintaining a pH between
7.35 and 7.45.
Calculating change in pH of buffer on addition of small amount of acid or alkali
If a small amount of alkali is added to a buffer then the moles of the buffer acid would reduce by the
number of moles of alkali added and the moles of salt would increase by the same amount so a new
calculation of pH can be done with the new values
CH3CO2H (aq) +OH-  CH3CO2- (aq) + H2O (l)
If a small amount of acid is added to a buffer then the moles of the buffer salt would reduce by the
number of moles of acid added and the moles of buffer acid would increase by the same amount so a
new calculation of pH can be done with the new values
CH3CO2- (aq) + H +  CH3CO2H (aq)
Example 12: 0.005 mol of NaOH is added to 500cm3 of a buffer where the concentration of ethanoic
acid is 0.200 mol dm-3 and the concentration of sodium ethanoate is 0.250 mol dm-3 . (Ka = 1.7 x 10-5)
Calculate the pH of the buffer solution after the NaOH has been added.
Work out the moles of acid and salt in the initial buffer solution
Moles ethanoic acid= conc x vol = 0.200 x 0.500 = 0.100mol
Moles sodium ethanoate = conc x vol = 0.25 x 0.500 = 0.125mol
Work out the moles of acid and salt in buffer after the addition of 0.005mol NaOH
Moles ethanoic acid = 0.100 - 0.005 = 0.095 mol
Moles sodium ethanoate = 0.125 +0.005 = 0.130 mol
[CH3COOH (aq)] acid and salt straight
[H+(aq)] = Ka into the equation as
[CH3COO- (aq) ] they both have the
same new final volume
0.095
0.130 = -log 1.24x 10-5
= 4.91
Titration curves
Constructing a pH curve
1. Transfer 25cm3 of acid to a conical flask with a volumetric Calibrate meter first by measuring known pH of a
pipette buffer solution. This is necessary because pH meters
2. Measure initial pH of the acid with a pH meter can lose accuracy on storage.
3. Add alkali in small amounts (2cm3) noting the volume Most pH probes are calibrated by putting probe in a
added set buffer (often pH 4) and pressing a calibration
4. Stir mixture to equalise the pH button/setting for that pH. Sometimes this is
5. Measure and record the pH to 1 d.p. repeated with a second buffer at a different pH
6. Repeat steps 3-5 but when approaching endpoint add in
Can also improve accuracy by maintaining
smaller volumes of alkali
constant temperature
7. Add until alkali in excess
Strong acid – Strong base

e.g. HCl and NaOH There are 4 main types of curve
1. Strong acid and strong base
pH
2. Weak acid and strong base
13 3. Strong acid and weak base
Long vertical part 4. Weak acid and weak base
from around 3 to 9
7
pH at equivalence point = 7
25 cm3 of base
You may also have to work out the

neutralisation volume from titration
data given in the question. These
are done by standard titration The equivalence point lies at the
calculations from module 1. mid point of the extrapolated
vertical portion of the curve.
The Key points to sketching a curve:

Initial and final pH
Volume at neutralisation
General Shape (pH at neutralisation)
Weak acid – Strong base e.g. CH3CO2H and NaOH
At the start the pH rises quickly and then Half neutralisation volume
levels off. The flattened part is called the For weak acids
buffer region and is formed because a buffer
solution is made [H+ (aq)][A- (aq)]
Ka=
pH [HA (aq)]
13
At ½ the neutralisation
volume the [HA] = [A-]
Equivalence point >7
So Ka= [H+] and pKa = pH
7
Steep part of curve >7 If we know the Ka we can then work

(around 7 to 9) out the pH at ½ V or vice versa
pH
starts 1
near 3 V cm3 of base

½V
Weak acid – Weak base
Strong acid – Weak base
e.g. HCl and NH3
e.g. CH3CO2H and NH3
pH
pH
13
13
No vertical part of the curve
Vertical part of curve

7 7
<7 (around 4 to 7)
Equivalence point < 7

1
1
25 cm3 of base
25 cm3 of base
Choosing an Indicator
HIn (aq) In- (aq) + H+ (aq)
Indicators can be considered as weak acids. The acid must colour A colour B
have a different colour to its conjugate base
We can apply Le Chatelier to give us the colour.
An indicator changes colour from HIn to In- over a
In an acid solution the H+ ions present will push
narrow range. Different indicators change colours
this equilibrium towards the reactants.
over different ranges.
Therefore colour A is the acidic colour.
The end-point of a titration is defined as the point when In an alkaline solution the OH- ions will react
the colour of the indicator changes colour and remove H+ ions causing the equilibrium to
shift to the products. Colour B is the alkaline
The end-point of a titration is reached when [HIn] = [In-].
colour.
To choose a correct indicator for a titration one should
pick an indicator whose end-point coincides with the
equivalence point for the titration.
An indicator will work if the pH range of the indicator lies on the vertical part of the titration curve. In this case the
indicator will change colour rapidly and the colour change will correspond to the neutralisation point.
pH
Only use phenolphthalein in titrations with strong strong base
bases but not weak bases- 13
Colour change: colourless acid  pink alkali pH range for

weak base phenolphthalein
7
Use methyl orange with titrations with weak acid pH range for methyl
strong acids but not weak acids orange
Colour change: red acid  yellow alkali 1
strong acid
(orange end point)
3
25 cm of base
Enthalpy change of Neutralisation

The standard enthalpy change of neutralisation is the enthalpy change when solutions of an acid and
an alkali react together under standard conditions to produce 1 mole of water.
Enthalpy changes of neutralisation are always exothermic. For reactions involving strong acids and alkalis, the
values are similar, with values between -56 and -58 kJ mol-1 because the same reaction is occurring H+ + OH-
H2O
Weak acids have a less exothermic enthalpy change of neutralisation because energy is absorbed to ionise the
acid and break the bond to the hydrogen in the un-dissociated acid.
8
13A: Lattice energy
Definitions of enthalpy changes for stages involved in forming an ionic lattice
Enthalpy change of formation

The standard enthalpy change of formation of a compound is the energy transferred when 1
mole of the compound is formed from its elements under standard conditions (298K and
100kpa), all reactants and products being in their standard states
Na (s) + ½Cl2 (g) NaCl (s) [∆f H= - 411.2 kJ mol-1]
Enthalpy of atomisation
The enthalpy of atomisation of an element is the enthalpy change when 1 mole of
gaseous atoms is formed from the element in its standard state
Na (s) Na(g) [∆atH = +148 kJ mol-1]
½ O2 (g) O (g) [∆atH = +249 kJ mol-1]
First Ionisation enthalpy Second Ionisation enthalpy

The first ionisation enthalpy is the enthalpy change The second ionisation enthalpy is the enthalpy
required to remove 1 mole of electrons from 1 mole change to remove 1 mole of electrons from one mole
of gaseous atoms to form 1 mole of gaseous ions of gaseous 1+ ions to produces one mole of gaseous
with a +1 charge 2+ ions.
Mg (g) Mg+ (g) + e- [∆H IE 1] Mg+ (g) Mg 2+ (g) + e- [∆H IE2 ]
First Electron Affinity Second Electron Affinity

The first electron affinity is the enthalpy change that
occurs when 1 mole of gaseous atoms gain 1 mole of The second electron affinity is the enthalpy change
electrons to form 1 mole of gaseous ions with a –1 when one mole of gaseous 1- ions gains one
charge electron per ion to produce gaseous 2- ions.
O (g) + e- O- (g) [∆Hea] = -141.1 kJ mol-1] O – (g) + e- O2- (g) [∆Hea = +798 kJ mol-1]
The first electron affinity is exothermic for atoms that The second electron affinity for oxygen is
normally form negative ions because the ion is more endothermic because it take energy to overcome
stable than the atom and there is an attraction the repulsive force between the negative ion and
between the nucleus and the electron the electron
First Electron affinity values will become less exothermic as you go down Group 7 from chlorine
to iodine because the atoms get bigger and have more shielding so it becomes less easy to
attract electrons to the atom to form the negative ion
Enthalpy of lattice formation

The Enthalpy of lattice formation is the standard enthalpy change when 1 mole
of an ionic crystal lattice is formed from its constituent ions in gaseous form.
Na+ (g) + Cl- (g) NaCl (s) [∆LEH = -787 kJ mol-1]
Trends in Lattice Enthalpies

The lattice enthalpies become
The strength of a enthalpy of lattice formation depends on the following less negative down any group.
factors e.g. LiCl, NaCl, KCl, RbCl
1. The sizes of the ions:
e.g group 1 halides (eg NaF KI) have
The larger the ions, the less negative the enthalpies of lattice lattice enthalpies of around –700 to -
formation (i.e. a weaker lattice). As the ions are larger the charges 1000
become further apart and so have a weaker attractive force group 2 halides (eg MgCl2) have lattice
between them. enthalpies of around –2000 to –3500
2. The charges on the ion: group 2 oxides eg MgO have lattice
The bigger the charge of the ion, the greater the attraction between enthalpies of around –3000 to –4500
the ions so the stronger the lattice enthalpy (more negative values). kJmol-1
BORN HABER CYCLES
The lattice enthalpy cannot be determined directly. We calculate it indirectly by making use of changes
for which data are available and link them together in an enthalpy cycle the Born Haber cycle
Born Haber cycle: sodium Chloride

Pay attention to state
symbols and direction of
Na+ (g) + e- + Cl (g)
arrows.
∆EaH (Cl)
∆atH (Cl)
Na+ (g) + Cl- (g) Usually all pieces of data are given
Na+(g) + e- + ½ Cl2(g) except the one that needs to be
calculated
∆IE 1H(Na)
∆ LE H (NaCl)
Na (g) + ½ Cl2(g)
∆atH (Na)
Na (s) + ½ Cl2(g)
∆fH (NaCl)
NaCl (s)
By applying Hess’s law the heat of formation equals to the sum of everything else
∆fH =∆atH (Na) + ∆IEH(Na)+ ∆atH(Cl) + ∆EaH(Cl) + ∆LEH
Rearrange to give ∆LEH = ∆fH - (∆atH (Na) + ∆IEH(Na)+ ∆atH (Cl) ∆EaH(Cl) )
∆LEH =-411 – (+107 + 496 + 122 + -349) = -787 kJmol-1
Born Haber cycle: magnesium Chloride

The data for the ∆at H (Cl) could
Mg2+ (g) + 2e- + 2Cl (g) also be given as the bond energy
for E(Cl-Cl ) bond.
2 x∆EaH(Cl)
2x ∆atH (Cl) Remember :
Mg2+ (g) + 2Cl- (g)
Mg2+ (g) + 2e- + Cl2(g) E(Cl-Cl ) = 2 x ∆at H (Cl)
∆IE 2H (Mg)
Note in this example the first and
second ionisation energies of
Mg+ (g) + e- + Cl2(g)
magnesium are needed as Mg is
∆IE 1H(Mg) a +2 ion
∆LEH
Mg (g) + Cl2(g)
∆atH (Mg)
Mg (s) + Cl2(g)
∆fH (MgCl2)
MgCl2 (s)
Born Haber cycle: calcium oxide
Ca2+ (g) + O2- (g)
Ca2+ (g) + 2e- + O (g)
∆Ea1H(O) Notice the second electron affinity
∆Ea1H (O) for oxygen is endothermic
∆atH(O) because it take energy to
Ca2+ (g) + e- + O- (g)
Ca2+ (g) + 2e- + ½ O2(g) overcome the repulsive force
between the negative ion and
∆IE2H (Ca) the electron
Ca + (g) + e- + ½ O2(g))
∆IE1H(Ca)
Ca (g) + ½ O2(g)
∆LEH
∆atH(Ca)
Ca (s) + ½ O2(g)
∆fH (CaO)
CaO (s)
Perfect Ionic Model
Theoretical lattice enthalpies assumes a perfect ionic model where the ions are 100% ionic and
spherical and the attractions are purely electrostatic.
Differences between theoretical and Born Haber (experimental) lattice enthalpies
The Born Haber lattice enthalpy is the real experimental value.

When a compound shows covalent character, the theoretical and the born Haber lattice enthalpies
differ. The more the covalent character the bigger the difference between the values.
When the negative ion becomes distorted and more covalent we say it becomes polarised. The
metal cation that causes the polarisation is called more polarising if it polarises the negative ion.
Ionic with covalent

100% ionic character + -
When 100 % ionic the ions are spherical. The charge cloud is distorted .The theoretical
The theoretical and the born Haber lattice and the experimental Born Haber lattice
enthalpies will be the same enthalpies will differ
The polarising power of cation increases when The polarizability of an anion depends
• the positive ion is small on its size. The bigger the ion the more
• the positive ion has multiple charges easily it is distorted
When a compound has some covalent character- it tends towards giant

covalent so the lattice is stronger than if it was 100% ionic. Therefore the
born haber value would be larger than the theoretical value.
Why does Calcium chloride have the formula CaCl2 and not CaCl or CaCl3?
It is useful to draw out the born haber cycles for each potential case. Theoretical lattice enthalpies have
been calculated for each case
We need to calculate an enthalpy of formation for each case.
The one with the most exothermic enthalpy of formation will be the one that Theoretical lattice enthalpies
forms as it will be the most thermodynamically stable ∆Hlatt CaCl = -719 kJ mol-1
∆Hlatt CaCl2 = -2218 kJ mol-1
∆Hlatt CaCl3 = -4650 kJ mol-1
Born Haber Cycle for CaCl
Ca+ (g) + e- + Cl (g) These get larger as the
positive charge on the
∆HEa(Cl)
∆atH (Cl) calcium ion becomes bigger.
Ca+ (g) + e- + ½ Cl2(g)
Ca+ (g) + Cl- (g)
∆HIE 1(Ca) The enthalpy of formation
is largely a balance of the
Ca (g) + ½ Cl2(g) ∆LEH ionisation energy and
∆atH (Ca) lattice enthalpy.
Ca (s) + ½ Cl2(g)
∆fH (CaCl) = -163.1 kJmol-1 ∆Hf (CaCl) is -163.1 kJ mol-1.
CaCl (s) This is exothermic.
Born Haber Cycle for CaCl2
Ca2+ (g) + 2e- + 2Cl (g)
2 x∆atH (Cl)
2 x∆HEa(Cl)
Ca2+ (g) + 2e- + Cl2(g)
∆HIE 2(Ca) Ca2+ (g) + 2Cl- (g)
The increased ionisation
Ca+ (g) + e- + Cl2(g) enthalpy to form Ca2+ is
more than compensated for
∆HIE 1(Ca) ∆LEH by the stronger lattice
enthalpy of formation
Ca (g) + Cl2(g)
The enthalpy of formation is
∆atH (Ca) therefore more exothermic.
Ca (s) + Cl2(g) This is the most stable form
∆fH (CaCl2) = -739.2 kJmol-1
CaCl2 (s)
Born Haber Cycle for CaCl3
Ca3+ (g) + 3e- + 3Cl (g)
3 x∆atH (Cl)
Ca3+ (g) + 3e- + 1.5 Cl2(g) 3 x∆HEa(Cl)
The big increase in ionisation
Ca3+ (g) + 3Cl- (g) enthalpy to remove the 3rd
electron is not compensated
for by the stronger lattice
∆HIE 3(Ca) enthalpy of formation
Ca2+ (g) + 2e- + 1.5 Cl2(g)
The enthalpy of formation is
∆HIE 2(Ca) ∆LEH therefore endothermic. This is
Ca+ (g) + e- + 1.5Cl2(g) the least stable form
∆HIE 1(Ca)
Ca (g) +1.5 Cl2(g)
CaCl3 (s)
∆atH (Ca)
Ca (s) + 1.5 Cl2(g) ∆fH (CaCl3) = +1541.7 kJmol-1 4
Solubility of ionic substances
Enthalpy of lattice formation Enthalpy of Hydration ∆Hhyd
The Enthalpy of lattice formation is the standard enthalpy • Enthalpy change when one mole of gaseous ions
change when 1 mole of an ionic crystal lattice is formed become hydrated such that further dilution causes no
from its constituent ions in gaseous form. further heat change
Na+ (g) + Cl- (g) NaCl (s) [∆LEH = -787 kJ mol-1]
X+ (g) + aq X+ (aq) For Li+ ∆hydH = -519 kJ mol-1
or
Enthalpy of solution
X- (g) + aq X- (aq) For F- ∆hydH = -506 kJ mol-1
The enthalpy of solution is the standard enthalpy change
when one mole of an ionic solid dissolves in an large
This always gives out energy (exothermic, -ve) because
enough amount of water to ensure that the dissolved ions
bonds are made between the ions and the water molecules
are well separated and do not interact with one another
NaCl (s) + aq Na+ (aq) + Cl-(aq)
Trends in Lattice Enthalpies

The lattice enthalpies become
The strength of a enthalpy of lattice formation depends on the following less negative down any group.
factors e.g. LiCl, NaCl, KCl, RbCl
1. The sizes of the ions:
e.g group 1 halides (eg NaF KI) have
The larger the ions, the less negative the enthalpies of lattice lattice enthalpies of around –700 to -
formation (i.e. a weaker lattice). As the ions are larger the charges 1000
become further apart and so have a weaker attractive force group 2 halides (eg MgCl2) have lattice
between them. enthalpies of around –2000 to –3500
2. The charges on the ion: group 2 oxides eg MgO have lattice
The bigger the charge of the ion, the greater the attraction between enthalpies of around –3000 to –4500
the ions so the stronger the lattice enthalpy (more negative values). kJmol-1
Enthalpies of solution Using Hess’s law to determine enthalpy changes of solution
When an ionic lattice dissolves in water it involves breaking up the bonds in the lattice and forming new
bonds between the metal ions and water molecules.
For MgCl2 the ionic equation for the dissolving is MgCl2 (s) + aq Mg2+ (aq) + 2Cl- (aq)
Mg2+ (g) + 2Cl- (g) When an ionic substance dissolves the lattice must be
broken up. The enthalpy of lattice dissociation is equal
∆hydH Mg2+ to the energy needed to break up the lattice (to gaseous
∆LEH(MgCl2) ions). This step is endothermic.
Mg2+ (aq) + 2Cl- (g)
The size of the lattice enthalpy depends on the size and
2 x ∆hydH Cl- charge on the ion. The smaller the ion and the higher its
MgCl2 (s)
charge the stronger the lattice
ΔHsolution
Mg2+ (aq) + 2Cl- (aq)
∆solH = - ∆LEH + Σ∆hydH
Example . Calculate the enthalpy of solution of NaCl Hydration enthalpies are exothermic as energy is given
given that the lattice enthalpy of formation of out as water molecules bond to the metal ions.
NaCl is -771 kJmol-1 and the enthalpies of
hydration of sodium and chloride ions are -406 The negative ions are attracted to the δ+ hydrogens on
and -364 kJmol-1 respectively the polar water molecules and the positive ions are
attracted to the δ- oxygen on the polar water molecules.
∆solH = - ∆LEH + Σ∆hydH
= - (-771) + (-406-364)
= + 1 kJmol-1
ΔH solution endothermic.
Ba2+ (g) + SO42- (g)
∆hydH Ba2+
The higher the charge density the greater the hydration
Ba2+ (aq) + SO42- (g) enthalpy (e.g. smaller ions or ions with larger charges)
∆LEH(BaSO4)
∆hydH SO42- as the ions attract the water molecules more strongly.
Ba2+ (aq) + SO42- (aq) e.g. Fluoride ions have more negative hydration
∆solH enthalpies than chloride ions
BaSO4 (s) INSOLUBLE
Magnesium ions have a more negative hydration enthalpy
than barium ions
What does ∆solH tell us?

Generally ∆solH is not very exo or endothermic so the hydration enthalpy is about the same as lattice enthalpy.
In general the substance is more likely to be soluble if the ∆solH is exothermic.
If a substance is insoluble it is often because the lattice enthalpy is much larger than the hydration enthalpy and
it is not energetically favourable to break up the lattice, making ∆solH endothermic.
We must consider entropy, however, to give us the full picture about solubility.
When a solid dissolves into ions the entropy increases as there is more disorder as solid changes to solution
and number of particles increases.
This positive ∆Ssystem can make ∆STotal positive even if ∆H solution is endothermic, especially at higher
temperatures.
For salts where ΔH solution is exothermic For salts where ΔH solution is endothermic
the salt will always dissolve at all Temperatures the salt may dissolve depending on whether the
∆S value is more positive than -∆H/T is negative
∆Stotal = -∆H/T + ∆Ssystem
∆Stotal = -∆H/T + ∆Ssystem
∆ Stotal is ∆Ssystem is positive
always ∆H is negative due to the Will dissolve
∆Ssystem is
positive so -∆H/T will increased disorder if ∆Stotal is ∆H is positive positive due to
always be as more particles negative so -∆H/T will the increased
positive
be negative disorder
Increasing the Temperature will make it more

likely that ∆STotal will become positive, making
the reaction feasible and the salt dissolve
13B Entropy
∆S)
Entropy change (∆
A SPONTANEOUS PROCESS (e.g. diffusion) will proceed on its

own without any external influence.
Activation
Energy:
Energy
A problem with ∆H EA
reactants
A reaction that is exothermic will result in products that
are more thermodynamically stable than the reactants.
This is a driving force behind many reactions and causes ∆H
them to be spontaneous (occur without any external products
influence).
Some spontaneous reactions, however, are endothermic. Progress of Reaction

How can this be explained?
We need to consider something called entropy
Entropy is a description of the number of
Entropy, S˚
ways atoms can share quanta of energy.
If number of ways of arranging the energy
(W) is high, then system is disordered
Substances with more ways of arranging their atoms and
and entropy (S) is high.
energy (more disordered) have a higher entropy.
System and Surroundings
When considering entropy it is useful to split the system

(the chemicals) from the surroundings. matter
A system will consist of reactants and then products. It does not change system
energy
temperature or pressure, and mass cannot be transferred to the
surroundings. Energy can be transferred to the surroundings.
surroundings
Entropy of the System, S˚system
Elements Compounds
Entropy
…tend to have lower gas

Simpler compounds Complex compounds
entropies than…
Pure substances Mixtures boiling
Liquid
Solids have lower entropies than liquids which are lower than gases. solid melting
When a solid increases in Temperature its entropy increases as the
particles vibrate more. Temperature
There is a bigger jump in entropy with boiling than that with melting.
Gases have large entropies as they are much more disordered At 0K substances have zero
entropy. There is no disorder
as particles are stationary
Predicting Change in entropy ‘∆Ssystem ’ Qualitatively
An increase in disorder and entropy will lead to a positive entropy change ∆S˚system = +ve
In general, a significant increase in the entropy will occur if:

Balanced chemical equations can
-there is a change of state from solid or liquid to gas
often be used to predict if ∆S˚system is
- there is a significant increase in number of molecules
positive or negative.
between products and reactants.
NH4Cl (s) HCl (g) + NH3 (g) Na s + ½ Cl2 g NaCl s

∆S˚system = +ve ∆S˚system = -ve
•change from solid reactant to gaseous products •change from gaseous and solid reactant to solid
•increase in number of molecules •decrease in number of molecules
both will increase disorder both will decrease disorder
Calculating ∆S˚system quantitatively
Data books lists standard entropies (S˚) per mole for a Elements in their standard states do not have zero
variety of substances. It is not possible for a substance entropy. Only perfect crystals at absolute zero
to have a standard entropy of less than zero. (T = 0 K) will have zero entropy:
The unit of entropy is J K-1 mol-1 ∆S˚system = Σ S˚products - ΣS˚reactants

Example
Calculate ∆S˚ for the following reaction at 25˚C:
S [Fe2O3] = 87.4 J K-1 mol-1
2Fe2O3 (s) + 3C (s) 4Fe (s) + 3CO2 (g) Note: the entropy
S [C] = 5.7 J K-1 mol-1
change is very positive
∆S˚system = ΣS˚products - ΣS˚reactants S [Fe] = 27.3 J K-1 mol-1 as a large amount of
= (3 x 213.6 + 4 x 27.3) – (2 x 87.4 + 3 x 5.7) gas is being created
S [CO2] = 213.6 J K-1 mol-1
increasing disorder
= + 558.1 J K-1 mol-1 = + 558 J K-1 mol-1 (3 S.F.)
Entropy of the Surroundings ∆Ssurrounding

The surroundings are the container, air, solvent.
In an endothermic reaction energy is transferred
In an exothermic reaction energy is given out into from the surroundings. The number of ways of
the surroundings. The number of ways of arranging the energy in the surroundings therefore
arranging the energy therefore increases and so decreases and so ∆Ssurrounding decreases and is
∆Ssurrounding increases and is positive. negative.
converted into Jmol-1 by x1000

∆Ssurrounding = - ∆H reaction
T in K
Convert oC into K
by +273
Total Entropy change ∆Stotal

∆Stotal = ∆Ssystem + ∆Ssurrounding
For any reaction to be spontaneous then ∆Stotal must be positive. If a reaction is not spontaneous
i.e. it doesn’t go, then ∆Stotal will be negative.
Example : Data for the following reaction, which represents the
reduction of aluminium oxide by carbon, are shown in the table. Substance ∆f H / ∆S /
Al2O3(s) + 3C(s) → 2Al(s) + 3CO(g) kJmol–1 JK–1mol–1
Calculate the values of ∆Ssystem, ∆H , ∆Ssurroundings and ∆STotal for the
above reaction at 298 K Al2O3(s) -1669 51
1. Calculate ∆Ssystem 2. Calculate ∆H˚ C(s) 0 6
∆S˚ = Σ S˚products - Σ S˚reactants ∆H˚ = Σ∆fH˚[products] - Σ∆fH˚ [reactants] Al(s) 0 28
= (2 x 28 + 3x198) – (51 + 3 x 6) = (3 x -111) – -1669 CO(g) -111 198

= +581 J K-1 mol-1 (3 S.F.) = +1336 kJ mol-1
3. Calculate ∆Ssurroundings 4. Calculate ∆STotal

∆Ssurrounding = - ∆H reaction ∆Stotal = ∆Ssystem + ∆Ssurrounding
T = 581 -4483
= -1336000/298 = -3902J K-1 mol-1
= - 4483 J K-1 mol-1
∆STotal is negative. The reaction is not feasible
Gibbs Free Energy Change, ∆G

Gibbs free energy is a term that
The balance between entropy and enthalpy determines the combines the effect of enthalpy
feasibility of a reaction. and entropy into one number
This is given by the relationship :
∆G = ∆H - T∆Ssystem A reaction that has increasing entropy
(+ve ∆Ssystem) and is exothermic (-ve
For any spontaneous change, ∆G will be negative.

∆H ) will make ∆G be negative and
will always be feasible
Convert from ˚C to K (+ 273) If ∆G is negative there is still a

Unit of S= J K-1 mol-1 possibility, however, that the reaction
will not occur or will occur so slowly that
∆G = ∆H - T∆Ssystem Need to convert to effectively it doesn’t happen.
KJ K-1 mol-1 If the reaction has a high activation
Units: KJ mol-1 ( ÷1000) energy the reaction will not occur.
Units: KJ mol-1
Example : Data for the following reaction, which represents the

reduction of aluminium oxide by carbon, are shown in the table. Substance ∆fH / ∆S /
Al2O3(s) + 3C(s) → 2Al(s) + 3CO(g) kJmol–1 JK–1mol–1
Calculate the values of ∆H , ∆S and ∆G for the above reaction at 298 K
Al2O3(s) -1669 51
1. Calculate ∆S 2. Calculate ∆H˚
C(s) 0 6
∆Ssystem ˚= Σ S˚products - Σ S˚reactants ∆H˚ = Σ∆ f H˚ [products] - Σ∆ f H˚ [reactants]
Al(s) 0 28
= (2 x 28 + 3x198) – (51 + 3 x 6) = (3 x -111) – -1669
CO(g) -111 198
= +581J K-1 mol-1 (3 S.F.) = +1336 kJ mol-1
3. Calculate ∆G
∆G = ∆H - T∆Ssystem
∆G is positive. The reaction is not feasible
= +1336 – 298x 0.581
= +1163kJ mol-1
9
Calculating the temperature a reaction will become
feasible ∆G during phase changes
Calculate the temperature range that this reaction will be As physical phase changes like melting and boiling are
feasible equilibria, the ∆G for such changes is zero.
N2(g) + O2(g) 2 NO(g)
∆ H = 180 kJ mol-1 ∆S = 25 J K-1 mol-1 What temperature would methane melt at?
The reaction will be feasible when ∆ G ≤0 CH4(s) CH4 (l) ∆H = 0.94 kJmol-1 ∆Ssystem = 10.3 Jmol-1K-1
Make ∆G = 0 in the following equation ∆G = ∆H - T∆Ssystem
0 = ∆H - T∆Ssystem Make ∆G = 0 in the following equation ∆G = ∆H - T∆Ssystem
0 = ∆H - T∆Ssystem
So T= ∆H / ∆Ssystem So T= ∆H /∆Ssystem
T = 180/ (25/1000) T= 0.94 / (10.3÷1000)
= 7200K
T= 91K
The T must be >7200K which is a high Temp!
Effect of Temperature on feasibility If the reaction involves an increase in entropy (∆S is +ve)
then increasing Temperature will make it more likely that
∆G = ∆H - T∆S
∆G is negative and more likely that the reaction
Changing Temperature will change the occurs e.g. NaCl + aq Na+(aq) + Cl-(aq)
value of - T∆S in the above equation
If the reaction has a ∆S close to zero then

If the reaction involves an decrease in entropy (∆S is -
temperature will not have a large effect on the
ve) then increasing Temperature will make it more less
feasibility of the reaction as - T∆S will be
likely that ∆G is negative and less likely for the
small and ∆G won’t change much
reaction to occur. E.g. HCl(g) + NH3 (g) ➝ NH4Cl(s)
e.g. N2 (g) + O2 (g) 2NO (g)
40
This graph shows how the free-energy change for formation
of ammonia varies with temperature above 240 K.
½ N2(g) + 3/2 H2(g) NH3(g) 30
20
Applying the equation of a straight line
ΔG kJ/ mol
y= mx+c to the ∆G = ∆H - T∆S equation. 10

c = ∆H
The gradient of this graph is equal to -∆S 0
0 200 400 600 800 1000
The positive gradient means ∆S is negative which -10 Temperature/ K
corresponds to the equation above showing
increasing order.
-20
When ∆G <0 then the reaction is spontaneous. In this
case at Temperatures below around 460K -30
The slope of the line would change below 240K because ammonia would be a liquid and the
entropy change would be different
Equilibrium constants and feasibility
Values of equilibrium constants can all be used to predict the extent a reaction might occur.
Reaction Reactants equal amounts Products Reaction goes
‘does not predominate in of products and predominate in to completion
go’ an equilibrium reactants an equilibrium
Kc < 10-10 Kc ≈ 0.1 Kc = 1 Kc≈ 10 Kc > 1010
ΔStotal increases the magnitude of the equilibrium constant increases since ΔG = - RT lnK
Where K is equilibrium constant Kc or Kp
This equation shows a reaction with a Kc >1 will therefore have a negative ΔG. Feasible
reactions with a negative ΔG will have large values for the equilibrium constant
If ΔG is negative it indicates a reaction might occur. There is still a possibility, however, that the reaction will not
occur or will occur so slowly that effectively it does not happen.
If the reaction has a high activation energy the reaction will not occur due to kinetic factors limiting the reaction.
14. Redox Equilibria
Electron
flow
Electrochemical cells
Salt bridge
•A cell has two half–cells. copper
•The two half cells have to be connected with a salt electrode
bridge. Zinc
•Simple half cells will consist of a metal (acts an electrode
electrode) and a solution of a compound containing
that metal (eg Cu and CuSO4). 1M
•These two half cells will produce a small voltage if 1M zinc copper
connected into a circuit. (i.e. become a Battery or sulphate sulphate
cell). solution solution
Why does a voltage form? Why use a High resistance

In the cell pictured above voltmeter?
When connected together the zinc half-cell has more of a tendency to The voltmeter needs to be of very
oxidise to the Zn2+ ion and release electrons than the copper half-cell. high resistance to stop the current
(Zn Zn2+ + 2e-) from flowing in the circuit. In this
More electrons will therefore build up on the zinc electrode than the state it is possible to measure the
copper electrode. maximum possible potential
A potential difference is created between the two electrodes. difference (E).
The zinc strip is the negative terminal and the copper strip is the The reactions will not be occurring
positive terminal. because the very high resistance
voltmeter stops the current from
This potential difference is measured with a high resistance voltmeter, flowing.
and is given the symbol E. The E for the above cell is E= +1.1V.
Salt Bridge
The salt bridge is used to connect up the circuit. The free moving ions conduct the charge.
A salt bridge is usually made from a piece of filter paper (or material) soaked in a salt solution, usually
Potassium Nitrate.
The salt should be unreactive with the electrodes and electrode solutions.. E.g. potassium chloride would not
be suitable for copper systems as Chloride ions can form complexes with copper ions.
A wire is not used because the metal wire would set up its own electrode system with the solutions.
What happens if current is allowed to flow?

If the voltmeter is removed and replaced with a bulb or if the circuit is short circuited, a current flows. The
reactions will then occur separately at each electrode. The voltage will fall to zero as the reactants are used up.
The most positive electrode will always undergo reduction.

Cu2+ (aq) + 2e-  Cu(s) (positive as electrons are used up)
The most negative electrode will always undergo oxidation.

Zn(s)  Zn2+ (aq) + 2e- (negative as electrons are given off)
Cell Diagrams
• The solid vertical line represents the boundary
Electrochemical cells can be represented by a cell diagram:
between phases e.g. solid (electrode) and
solution (electrolyte)
Zn(s) | Zn2+ (aq) | | Cu2+ (aq) | Cu (s) E= +1.1V
•The double line represents the salt bridge
between the two half cells
Most oxidised form is put next to the double line
•the voltage produced is indicated
•the more positive half cell is written on the right
if possible (but this is not essential)
Systems that do not include metals.

If a system does not include a metal that can act as an electrode, then a platinum electrode must be used
and included in the cell diagram. It provides a conducting surface for electron transfer
A platinum electrode is used because it is unreactive and can conduct electricity.
e.g. for Fe2+ (aq)  Fe3+ (aq) + e- there is no If the system contains several species
solid conducting surface, a Pt electrode must be e.g. MnO4- + 8H+ + 5e- Mn2+ + 4H2O
used. then in the cell diagram the balancing numbers, H+
ions and H2O can be left out.
The cell diagram is drawn as:
| | Fe3+ (aq), Fe2+ (aq) |Pt | |MnO4- , Mn2+ |Pt
or if on left hand side
Still with more oxidised form near double line Pt | Mn2+ , MnO4- | |
A comma separates the oxidised from the reduced
species.
If a half equation has several physical states then the solid vertical
line should be used between each different state boundary.
4e- + 2H2O (l) +O2 (g) 4OH- (aq) | | O2 | H2O, OH- | Pt
Cl2 (g) + 2e-  2Cl- (aq) | | Cl2 | Cl- | Pt
As the phase line also separates the oxidised and

reduced terms a comma is not necessary here.
Measuring the electrode potential of a cell
• It is not possible to measure the absolute potential of a half electrode on its own. It is
only possible to measure the potential difference between two electrodes.
• To measure it, it has to be connected to another half-cell of known potential, and the
potential difference between the two half-cells measured.
• by convention we can assign a relative potential to each electrode by linking it to a
reference electrode (hydrogen electrode), which is given a potential of zero Volts
The standard hydrogen electrode
The potential of all electrodes are measured by comparing

their potential to that of the standard hydrogen electrode. Metal
Salt bridge
electrode
H2 gas at KNO3 (aq)
e.g. Fe
The standard hydrogen electrode (SHE) is assigned the 100kPa
potential of 0 volts.
Pt electrode
The hydrogen electrode equilibrium is:
H2 (g) 2H+ (aq) + 2e-
1M HCl
In a cell diagram the hydrogen electrode is
represented by: Pt |H2 (g) | H+ (aq)
Solution containing metal
ions (e.g. Fe2+) at 1 mol
Components of a standard hydrogen electrode. dm-3 concentration
To make the electrode a standard reference electrode
some conditions apply: Because the equilibrium does not include a
1. Hydrogen gas at pressure of 100 kPa conducting metal surface a platinum wire is used
2. Solution containing the hydrogen ion at 1.00 mol dm-3 which is coated in finely divided platinum. (The
(solution is usually 1M HCl) platinum black acts as a catalyst, because it is
3. Temperature at 298K porous and can absorb the hydrogen gas.)
Secondary standards
Standard conditions are needed because
The Standard Hydrogen Electrode is difficult to use, so often a
the position of the redox equilibrium will
different standard is used which is easier to use.
change with conditions.
These other standards are themselves calibrated against the SHE.
For example, in the equilibrium:
This is known as using a secondary standard - i.e. a standard
Mn+(aq) + n e- M(s)
electrode that has been calibrated against the primary standard.
The common ones are:
an increase in the concentration of Mn+
silver / silver chloride E = +0.22 V
would move the equilibrium to the right,
calomel electrode E = +0.27 V
so making the potential more positive.
Standard Electrode Potentials E

The standard conditions are :
When an electrode system is connected to the •All ion solutions at 1 1.00 mol dm-3
hydrogen electrode system, and standard conditions •temperature 298K
apply the potential difference measured is called the •gases at 100kPa pressure
standard electrode potential, •No current flowing
Salt bridge
Standard electrode potentials are found in KNO3 (aq)
data books and are quoted as H2 gas at
100kPa
Li+(aq) | Li (s) E= -3.03V Pt electrode
more oxidised form on left
They may also be quoted as half Pt electrode

equations
Li+ (aq) + e- Li (s) E= -3.03V
but again the more oxidised form is on 1M HCl
the left
Pt|H2|H+||Fe3+,Fe2+|Pt 1M Fe2+ and 1M Fe3+
Note: in the electrode system containing two solutions it is

necessary to use a platinum electrode and both solutions must
be of a 1M concentration.
3
Calculating the EMF of a cell
In order to calculate the Ecell, we must use ‘standard
Mg(s) | Mg2+ (aq) | | Cu2+ (aq) | Cu (s) E= +1.1V electrode potentials’ for the half cells.
use the equation Ecell= Erhs - Elhs Each half cell has a standard
electrode potential value
For the cell diagram above Mg2+ (aq)| Mg(s) E= -2.37V
Ecell = 0.34 - -2.37 Cu2+ (aq) | Cu (s) E = +0.34V
= + 2.71 V
Using electrode potentials
The most useful application of electrode potentials is to show

the direction of spontaneous change for redox reactions
The easiest way to use electrode potentials is as follows:
For any two half equations The more negative half cell will
always oxidise (go backwards)
If we want to work out the Ecell
Mg2+ (aq) + 2e-  Mg(s) E= -2.37V that corresponds to this
Cu2+ (aq) + 2e-  Cu (s) E = +0.34V spontaneous change then use
The reaction would be Ecell = Ered – Eox
The more positive half cell will always Mg + Cu2+  Cu + Mg 2+ A spontaneous change will
reduce (go forwards) always have a positive Ecell
The most negative electrode will oxidise and go from right to left
Zn2+(aq) + 2e-  Zn(s) E= - 0.76V
The half equation is therefore Zn(s)  Zn2+ (aq) +2e-
Fe2+(aq) + 2e-  Fe(s) E= -0.44V
Electrons are given off (lost) and travel to positive electrode
To get the full equation of the reaction add the

The more positive electrode will reduce and go from left to
two half reactions together, cancelling out the
right Fe2+ (aq) +2e-  Fe(s)
electrons.
Electrons arrive at this electrode and are absorbed (gained)
Zn + Fe2+  Fe + Zn2+
Using series of standard electrode potentials

Most strong reducing
oxidation agents found here
As more +ve As more -ve

Li+ + e-  Li -3.03V
increasing increasing
Mn2+ + 2e-  Mn -1.19V
tendency for tendency for
species on left to species on right
reduce, and act to oxidise, and
2H+ + 2e-  H2 0V
as oxidising act as reducing
agents agents
Ag+ + e-  Ag +0.8V
F2 + 2e-  2F- +2.87
Most strong oxidising reduction If we want to work out the Ecell from two
agents found here standard electrode potentials then use
Ecell = Ered – Eox
The most powerful reducing agents will be found at the most negative end of the series
on the right (ie the one with the lower oxidation number)
The most powerful oxidising agents will be found at the most positive end of the series on
the left (ie the one with the higher oxidation number)
4
Example 1
Use electrode data to explain why fluorine reacts with water.

Write an equation for the reaction that occurs.
oxidise
O2(g) + 4H+(aq) + 4e– → 2H2O(I) Eo+1.23V
First apply idea that more positive Eo will reduce (go forward)
F2(g) + 2e– → 2F–(aq) Eo +2.87V
and more negative Eo will oxidise (go backwards)
reduce
Explanation to write
As Eo F2/F- > Eo O2/H2O, and Ecell is a positive work out Ecell and quote it as part of your
value of +1.64V, F2 will oxidise H2O to O2 answer
Ecell = Ered - Eox = 2.87-1.23 =1.64V
Equation Remember to cancel out electrons in full equation

2F2(g) + 2H2O(I) → 4F–(aq) + O2(g) + 4H+(aq)
Example 2
Cl2(aq) + 2e– → 2Cl–(aq) Eo+1.36V
Use data from the table to explain why chlorine
2HOCl(aq) + 2H (aq) + 2e → Cl2(aq) + 2H2O(I) Eo+1.64V
+ –
should undergo a redox reaction with water. Write
H2O2(aq) + 2H+(aq) + 2e– → 2H2O(I) Eo +1.77V
an equation for this reaction. + –
O2(g) + 4H (aq) + 4e → 2H2O(I) Eo +1.23V
reduce
First select relevant half equations by considering the Eo
values and applying the idea that more positive Eo will reduce Cl2(aq) + 2e– → 2Cl– (aq) Eo+1.36V
(go forward) and more negative Eo will oxidise (go backwards) O2(g) + 4H (aq) + 4e → 2H2O(I) Eo +1.23V
+ –
oxidise
Explanation to write
Equation
As Eo Cl2/Cl- > Eo O2/H2O, and Ecell is a positive
value of +0.13V, Cl2 will oxidise H2O to O2 2Cl2(g) + 2H2O(I) → 4Cl–(aq) + O2(g) + 4H+(aq)
Example 3
Suggest what reactions occur, if any, when hydrogen gas Fe3+ (aq) + e– → Fe2+ (aq) Eo +0.77V
is bubbled into a solution containing a mixture of iron(II) 2H+(aq) + 2e– → H2(g) Eo 0.00V
and iron(III) ions. Explain your answer. Fe2+ (aq) + 2e– → Fe(s) Eo–0.44V
reduce
First select relevant half equations by considering the Eo
values and applying the idea that more positive Eo will reduce Fe3+ (aq) + e– → Fe2+ (aq) Eo +0.77V
(go forward) and more negative Eo will oxidise (go backwards) 2H+(aq) + 2e– → H2(g) Eo 0.00V
Explanation to write oxidise

Fe3+ will be reduced to Fe2+ by H2 oxidising to H+
Equation
because Eo Fe3+ /Fe2+ > Eo H+/H2 and Ecell is a
positive value of +0.77V 2Fe3+ (aq) + H2(g) → 2Fe2+ (aq) + 2H+(aq)
Example 4 Disproportionation
Use the half-equations to explain in terms of oxidation states what
happens to hydrogen peroxide when it is reduced.
reduce
Explanation to write H2O2(aq) + 2H+(aq) + 2e– → 2H2O(I) Eo+1.77V
O2(g) + 2H+(aq) + 2e– → H2O2(aq) Eo +0.68V
As Eo H2O2/H2O > Eo O2/H2O2 and Ecell is a positive
value of +1.09V , H2O2 disproportionates from -1 oxidise
oxidation state to 0 in O2 and -2 in H2O Equation
2H2O2(aq) → O2 + 2H2O(I)
Disproportionation of copper(I) iodide
Copper(I) iodide when reacting with sulphuric acid will disproportionate to Cu2+ and Cu metal
2Cu+  Cu + Cu2+
Cu+(aq) + e−  Cu(s) Eo = +0.52 V As Eo Cu+/Cu > Eo Cu2+/Cu+ and Ecell has a positive
Cu2+(aq) + e−  Cu+(aq) Eo = +0.15 V value of +0.37V , Cu+ disproportionates from +1
So Eo cell = 0.52 − 0.15 = +0.37 V oxidation state to 0 in Cu and +2 in Cu2+
Ecell is directly proportional to the total entropy change

and to lnK (where K is equilibrium constant)for a reaction
A positive Ecell will lead to a positive total entropy change
Effect of conditions on Cell voltage Ecell
The effects of changing conditions on E cell can be Ecell is a measure of how far from equilibrium the
made by applying le Chatelier’s principle. cell reaction lies. The more positive the Ecell the
more likely the reaction is to occur.
If current is allowed to flow, the cell reaction will occur
and the Ecell will fall to zero as the reaction proceeds
and the reactant concentrations drop.
Zn2+(aq) + 2e-  Zn(s) E= - 0.76V
Effect of concentration on Ecell Fe2+(aq) + 2e-  Fe(s) E= -0.44V
Looking at cell reactions is a straight forward Zn + Fe2+  Fe + Zn2+ E= +0.32

application of le Chatelier. So increasing
Increasing the concentration of Fe2+ and
concentration of ‘reactants’ would increase Ecell and
decreasing the concentration of Zn2+ would
decreasing them would cause Ecell to decrease.
cause Ecell to increase.
Effect of temperature on Ecell
Most cells are exothermic in the spontaneous direction so applying Le Chatelier to a temperature rise to these
would result in a decrease in Ecell because the equilibrium reactions would shift backwards.
If the Ecell positive it indicates a reaction might occur. There is still a possibility, however, that the reaction will
not occur or will occur so slowly that effectively it does not happen.
If the reaction has a high activation energy the reaction will not occur.
Also if the reaction is carried out at non-standard conditions the Ecell using standard conditions may deviate
Cells
You should be able to
Electrochemical cells can be used as a commercial source of electrical energy work out Ecell for given
Cells can be non-rechargeable (irreversible), rechargeable and fuel cells. half reactions.
You do not need to learn the details of most of these cells. Relevant cell information will be given. You
should be able to convert between standard electrode potential half cells, full cell reactions and cell
diagrams and be able to calculate potentials from given data.
Example primary non rechargeable cells Cells are non-rechargeable when the reactions
that occur with in them are non-reversible.
Dry Cell Zn2+(aq) + 2e-  Zn(s) E = - 0.76 V More negative half equation will oxidise
2MnO2(s) + 2NH4+(aq) +2 e- → Mn2O3(s) + 2NH3(aq) + H2O(l) E = 0.75 V
Overall reaction 2MnO2 + 2NH4++ Zn → Mn2O3 + 2NH3 + H2O + Zn2+ Ecell =+1.51V
Example primary Lithium –manganese dioxide cell- non rechargeable

Li+aq +e-  Li (s) E = - 3.04 V More negative half equation will oxidise
Li+aq + MnO2 (s) +e-  LiMnO2(s) E = - 0.13 V (Mn will reduce changing oxidation state from +4 to +3)
Overall reaction Li + MnO2 → LiMnO2
Ecell = E red- Eox = -0.13 - - 3.04 = 2.91 V
Conventional cell
Li (s)| Li+aq | | Li+aq | MnO2 (s) , LiMnO2(s) | Pt (s) Ecell =+2.91V
diagram
Example secondary rechargeable cells The forward reaction occurs on

discharge giving out charge.
Charging causes the reaction to
Lead acid Cell PbSO4 + 2e-  Pb + SO42- E= -0.356V reverse
PbO2 + SO42- + 4H+ + 2e-  PbSO4 + 2H2O E= +1.685 V Reversible cells only
work if the product stays
Overall reaction PbO2 +Pb + 2SO42- + 4H+  2 PbSO4 + 2H2O Ecell= +2.04V
attached to the electrode
and does not disperse
Example secondary Nickel–cadmium cells are used to power electrical equipment such as drills and shavers.
They are rechargeable cells.
The electrode reactions are shown below.
NiO(OH) + H2O + e-  Ni(OH)2 + OH– E = +0.52 V (Ni will reduce changing oxidation state from 3 to 2)
Cd(OH)2 + 2e-  Cd + 2OH– E = –0.88 V (Cd will oxidise changing oxidation state from 0 to 2)
Overall reaction discharge 2NiO(OH) + Cd + 2H2O  2Ni(OH)2 + Cd(OH)2 E= +1.40V

Ecell = E red- Eox = +0.52 - - 0.88 = + 1.40 V
Example secondary Lithium ion cells are used to power cameras and mobile phones.
Li+ + CoO2 + e-  Li+[CoO2] - E=+0.6V (Co will reduce changing oxidation state from 4 to 3
Li+ + e-  Li E=-3.0V
The reagents in the cell are absorbed onto
powdered graphite that acts as a support
Overall discharge Li + CoO2  LiCoO2 E=3.6V
medium. The support medium allows the ions
reaction
Conventional cell to react in the absence of a solvent such as
Li | Li+ || Li+ , CoO2 | LiCoO2 | Pt water.
diagram
The overall reaction would be reversed Water would not be good as a solvent as it
in the recharging state would react with the lithium metal.
Fuel cell
A fuel cell uses the energy from the reaction of
a fuel with oxygen to create a voltage
Hydrogen Fuel cell (potassium hydroxide electrolyte)
4e- + 4H2O  2H2 +4OH- E=-0.83V H2 O2

4e- + 2H2O +O2  4OH- E=+0.4V from from air
fuel
Overall reaction 2H2 + O2  2H2O E=1.23V
2e- + 2H+ H2 E=0V In acidic conditions these are the

electrode potentials. The Ecell is H2O
4e- + 4H+ +O2  2H2O E=1.23V
the same as alkaline conditions as +heat
Overall 2H2 + O2  2H2O E=1.23V the overall equation is the same
Using standard conditions: The rate is too
slow to produce an appreciable current.
Fuel cells will maintain a constant voltage over time as they are Higher temperatures are therefore used to
continuously fed with fresh O2 and H2 so maintaining constant increase rate but the reaction is exothermic
so by applying le chatelier would mean the
concentration of reactants. This differs from ordinary cells where
emf falls.
the voltage drops over time as the reactant concentrations drop A higher pressure can help counteract this
Advantages of Fuel cells over conventional Limitations of hydrogen fuel cells

petrol or diesel-powered vehicles (i) expensive
(i) less pollution and less CO2. (Pure hydrogen (ii) storing and transporting hydrogen, in terms of
emits only water whilst hydrogen-rich fuels safety, feasibility of a pressurised liquid and a limited
produce only small amounts of air pollutants and life cycle of a solid ‘adsorber’ or ‘absorber’
CO2). (iii) limited lifetime (requiring regular replacement and
(ii) greater efficiency; disposal) and high production costs,
(iv) use of toxic chemicals in their production
Hydrogen is readily available by the

Hydrogen can be stored in fuel cells
electrolysis of water, but this is
(i) as a liquid under pressure,
expensive. To be a green fuel the
(ii) adsorbed on the surface of a solid material,
electricity needed would need to be
(iii) absorbed within a solid material;
produced from renewable resources
Ethanol fuel cells
Ethanol fuel cells have also been developed. Compared to

Equation that occurs at oxygen electrode
hydrogen fuel cells they have certain advantages including.
4e- + 4H+ +O2  2H2O E=1.23V
Ethanol can be made from renewable sources in a carbon
neutral way Equation that occurs at ethanol electrode
Raw materials to produce ethanol by fermentation are C2H5OH + 3H2O → 2CO2 + 12H+ + 12e-
abundant
Ethanol is less explosive and easier to store than hydrogen. Overall equation
New petrol stations would not be required as ethanol is a C2H5OH + 3O2 → 2CO2 + 3H2O
liquid fuel.
Methanol can also be used in fuel cells
Redox titrations
Manganate redox titration
The purple colour of manganate can make it
The redox titration between Fe2+ with MnO4– (purple) is a very
difficult to see the bottom of meniscus in
common exercise. This titration is self indicating because of the
the burette
significant colour change from reactant to product
If the manganate is in the burette then the
MnO4-(aq) + 8H+ (aq) + 5Fe2+ (aq)  Mn2+ (aq) + 4H2O (l) + 5Fe3+ (aq) end point of the titration will be the first
Purple colourless permanent pink colour
Colourless  purple
Choosing correct acid for manganate titrations.
The acid is needed to supply the 8H+ ions. Some acids are not suitable as they set up alternative redox
reactions and hence make the titration readings inaccurate.
Only use dilute sulphuric acid for manganate titration
Insufficient volumes of sulphuric acid will mean the solution is not acidic enough and MnO2 will be produced
instead of Mn2+
MnO4-(aq) + 4H+(aq) + 3e-  MnO2 (s) + 2H2O
The brown MnO2 will mask the colour change and lead to a greater (inaccurate) volume of Manganate being
used in the titration
Using a weak acid like ethanoic acid would have the same effect as it cannot supply the large amount of
hydrogen ions needed (8H+)
It cannot be conc HCl as the Cl- ions would be oxidised to Cl2 by MnO4- as the Eo MnO4-/Mn2+ > Eo Cl2/Cl-
MnO4-(aq) + 8H+(aq) + 5e–  Mn2+ (aq) + 4H2O(l) E+1.51V
Cl2(aq) +2e–  2Cl–(aq) E +1.36V
This would lead to a greater volume of manganate being used and poisonous Cl2 being produced
It cannot be nitric acid as it is an oxidising agent. It oxidises Fe2+ to Fe3+ as Eo NO3-/HNO2> Eo Fe3+/Fe2+
NO3- (aq) + 3H+(aq) + 2e–  HNO2(aq) + H2O(l) Eo +0.94V
Fe3+ (aq)+e–  Fe2+ (aq) Eo +0.77 V
This would lead to a smaller volume of manganate being used
be able to perform calculations for these titrations and for

others when the reductant and its oxidation product are given.
Manganate titration example Step1 : find moles of KMnO4
A 2.41g nail made from an alloy containing iron is moles = conc x vol
dissolved in 100cm3 acid. The solution formed 0.02 x 9.8/1000
contains Fe(II) ions. = 1.96x10-4 mol
10cm3 portions of this solution are titrated with Step 2 : using balanced equation find moles Fe 2+ in 10cm3
potassium manganate (VII) solution of 0.02M. = moles of KMnO4 x 5
9.80cm3 of KMnO4 were needed to react with the
= 9.8x10-4 mol
solution containing the iron.
Step 3 : find moles Fe2+ in 100cm3
What is the percentage of Iron by mass in the nail?
= 9.8x10-4 mol x 10
MnO4-(aq) + 8H+(aq) + 5Fe2+  Mn2+(aq) + 4H2O + 5Fe3+ = 9.8x10-3 mol
Step 4 : find mass of Fe in 9.8x10 -3 mol
mass= moles x RAM = 9.8x10-3 x 55.8 = 0.547g
Step 5 ; find % mass
%mass = 0.547/2.41 x100
= 22.6%
9
Other useful manganate titrations
With hydrogen peroxide
Ox H2O2  O2 + 2H+ + 2e-
Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O The reaction between MnO4- and
Overall 2MnO4-(aq) + 6H+(aq) + 5H2O2  5O2 + 2Mn2+ (aq) + 8H2O C2O42- is slow to begin with (as
With ethanedioate the reaction is between two
negative ions) To do as a titration
Ox C2O42-  2CO2 + 2e-
the conical flask can be heated to
Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O
60o C to speed up the initial
Overall 2MnO4-(aq) + 16H+(aq) + 5C2O42-(aq)  10CO2(g) + 2Mn2+(aq) + 8H2O(l)
reaction.
With Iron (II) ethanedioate both the Fe2+ and the C2O42- react with the MnO4-
1MnO4- reacts with 5Fe2+ and 2 MnO4- reacts with 5C2O42-
MnO4-(aq) + 8H+(aq) + 5Fe2+  Mn2+ (aq) + 4H2O + 5Fe3+

2MnO4-(aq) + 16H+(aq) + 5C2O42-  10CO2 + 2Mn2+ (aq) + 8H2O
So overall
3MnO4-(aq) + 24H+(aq) + 5FeC2O4  10CO2 + 3Mn2+ (aq) + 5Fe3+ + 12H2O
So overall the ratio is 3 MnO4- to 5 FeC2O4
Step1 : find moles of KMnO4

A 1.412 g sample of impure FeC2O4.2H2O
moles = conc x vol
was dissolved in an excess of dilute
sulphuric acid and made up to 250 cm3 of 0.0189 x 23.45/1000
solution. 25.0 cm3 of this solution = 4.43x10-4 mol
decolourised 23.45 cm3 of a 0.0189 mol Step 2 : using balanced equation find moles FeC 2O4.2H2O in 25cm3
dm–3 solution of potassium = moles of KMnO4 x 5/3 (see above for ratio)
manganate(VII). = 7.39x10-4 mol
What is the percentage by mass of Step 3 : find moles FeC2O4.2H2O in 250 cm3
FeC2O4.2H2O in the original sample? = 7.39x10-4 mol x 10
= 7.39x10-3 mol
Step 4 : find mass of FeC2O4.2H2O in 7.39x10-3 mol
mass= moles x Mr = 7.39x10-3 x 179.8 = 1.33g
Step 5 ; find % mass
%mass = 1.33/1.412 x100
= 94.1%
Thiosulphate redox titration A starch indicator is added near the end

The redox titration between I2 and thiosulphate S2O32- is a point when the iodine fades a pale yellow
common exercise. to emphasise it.
With starch added the colour change is
2S2O32-(aq) + I2 (aq)  2I- (aq) + S4O62-(aq) from blue/black to colourless
yellow/brown sol colourless sol
The starch should not be added until nearly all the iodine has
reacted because the blue complex formed with high
concentrations of iodine is insoluble and does not re-dissolve as
more thiosulfate is added
Errors
Calculating apparatus errors

Each type of apparatus has a sensitivity error
To decrease the apparatus errors you
•balance  0.001 g can either decrease the sensitivity error
•volumetric flask  0.1 cm3 by using apparatus with a greater
•25 cm3 pipette  0.1 cm3 resolution (finer scale divisions ) or you
•burette  0.05 cm3 can increase the size of the
measurement made.
Calculate the percentage error for each piece of equipment used by
If looking at a series of measurements
% error =  sensitivity error x 100 in an investigation the experiments with
Measurement made on apparatus the smallest readings will have the
highest experimental errors.
e.g. for pipette
% error = 0.05/ 25 x100
If the burette used in the titration had
To calculate the maximum percentage apparatus error in the final an uncertainty for each reading of
result add all the individual equipment errors together. +/– 0.05 cm3 then during a titration
two reading would be taken so the
error on the titre volume would be
Reducing errors in a titration +/– 0.10 cm3
Replacing measuring cylinders with pipettes or burettes which have

lower apparatus sensitivity error will lower the error
To reduce the error in a burette reading it is necessary to make the

titre a larger volume. This could be done by: increasing the volume
and concentration of the substance in the conical flask or by
decreasing the concentration of the substance in the burette.
Reducing errors in measuring mass

Using a more accurate balance or a larger mass will
reduce the error in weighing a solid
Weighing sample before and after addition and then
calculating difference will ensure a more accurate
measurement of the mass added.
Calculating the percentage difference between the If the %error due to the apparatus < percentage
actual value and the calculated value difference between the actual value and the
calculated value then there is a discrepancy in
If we calculated an Mr of 203 and the real value is 214, the result due to other errors.
then the calculation is as follows:
Calculate difference 214-203 = 11 If the %error due to the apparatus > percentage
% = 11/214 x100 difference between the actual value and the
=5.41% calculated value then there is no discrepancy
and all errors in the results can be explained by
the sensitivity of the equipment.
16. Kinetics II
The rate of reaction is defined as the change in concentration of a substance in unit time
Its usual unit is mol dm-3s-1
When a graph of concentration of reactant is plotted vs Initial rate =

time, the gradient of the curve is the rate of reaction. gradient of
concentration
tangent
The initial rate is the rate at the start of the
reaction where it is fastest
Reaction rates can be calculated from graphs of

concentration of reactants or products
time
Techniques to investigate rates of reaction
There are several different methods for measuring reactions rates. Some reactions can be measured
in several ways
measurement of the change in volume of a gas
This works if there is a change in the number of moles of
gas in the reaction. Using a gas syringe is a common
way of following this. If drawing a gas syringe make
sure you draw it with some
(CH3)2C=CH2(g) + HI(g) (CH3)3CI(g) measurement markings on the
barrel to show measurements
HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g) can be made.
Measurement of change of mass
This works if there is a gas produced which is allowed to

escape. Works better with heavy gases such as CO2
HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g)
Titrating samples of reaction mixture with acid, alkali, sodium thiosulphate etc
Small samples are removed from the reaction mixture, quenched (which
stops the reaction) and the titrated with a suitable reagent.
HCOOCH3(aq) + NaOH(aq)  HCOONa(aq) + CH3OH(aq) The NaOH could be titrated with an acid
BrO3 –(aq) + 5Br –(aq) + 6H+(aq)  3Br2(aq) + 3H2O(l) The H+ could be titrated with an alkali
CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I–(aq) The I2 could be titrated with sodium
thiosulphate
Colorimetry.
If one of the reactants or products is coloured H2O2(aq) + 2I- (aq) + 2H+(aq)  2H2O(l) + I2(aq)
then colorimetry can be used to measure the
change in colour of the reacting mixtures The I2 produced is a brown solution
Measuring change in electrical conductivity

Can be used if there is a change in the number HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g)
of ions in the reaction mixture
Measurement of optical activity.

If there is a change in the optical activity through
the reaction this could be followed in a CH3CHBrCH3 (l) + OH−(aq)  CH3CH(OH)CH3 (l) + Br−(aq)
polarimeter
Rate Equations
The rate equation relates mathematically the rate of reaction to the concentration of the reactants.
For the following reaction, aA + bB  r is used as symbol for rate

products, the generalised rate equation is: r = k[A]m[B]n
The unit of r is usually mol dm-3 s-1
The square brackets [A] means

m, n are called reaction orders the concentration of A
Orders are usually integers 0,1,2 (unit mol dm-3)
0 means the reaction is zero order with respect to that reactant k is called the rate constant
1 means first order
2 means second order
The total order for a reaction is worked
NOTE: the orders have nothing to do with the stoichiometric out by adding all the individual orders
coefficients in the balanced equation. They are worked out together (m+n)
experimentally
Calculating orders from initial rate data
For zero order: the concentration of A has no effect on the

initial
rate of reaction r = k[A]0 = k
For first order: the rate of reaction is directly proportional

to the concentration of A r = k[A]1
For second order: the rate of reaction is proportional to the

concentration of A squared r = k[A]2
For a rate concentration graph to show the

Graphs of initial rate against concentration show the
order of a particular reactant the
different orders. The initial rate may have been
concentration of that reactant must be varied
calculated from taking gradients from concentration
whilst the concentrations of the other
/time graphs
reactants should be kept constant.
Continuous rate experiments

Continuous rate data
0.060 This is data from one experiment where the concentration

of one substance is followed throughout the experiment.
If half-lives are constant
[A]
then the order is 1st order

For this method to work the concentrations of the
0.030 reactants not being followed must be in large excess in
the experiment so their concentrations stay virtually
constant and do not affect rate.
0.015
0.0075
This data is processed by plotting the data and calculating
successive half-lives.
t½ t½ t½
Time (min) The half-life of a first-order reaction
is independent of the concentration and is constant
Second order zero order
0.060
0.060 If zero order the rate
stays constant as the
reactant is used up.
This means the
[A]
If half-lives rapidly increase
concentration has no
[A]
0.030 then the order is 2nd order

0.030 effect on rate
0.015
0.015
0.0075
0.0075
t½ t½ t½
Time (min) Time (min)
The rate constant (k)
1. The units of k depend on the overall order of For a 1st order overall reaction the unit of k is
reaction. It must be worked out from the rate s-1
equation For a 2nd order overall reaction the unit of k is
2. The value of k is independent of concentration and mol-1dm3s-1
time. It is constant at a fixed temperature. For a 3rd order overall reaction the unit of k is
3. The value of k refers to a specific temperature and mol-2dm6s-1
it increases if we increase temperature
Example (first order overall)
Rate = k[A][B]0 m = 1 and n = 0 Remember: the values of the reaction orders must
- reaction is first order in A and zero order in B be determined from experiment; they cannot be
- overall order = 1 + 0 = 1 found by looking at the balanced reaction equation
- usually written: Rate = k[A]
Calculating units of k
1. Rearrange rate equation 2. Insert units and

to give k as subject cancel
k = Rate k = mol dm-3s-1

Unit of k = s-1
[A] mol dm-3
Example: Write rate equation for reaction between A and B

where A is 1st order and B is 2nd order.
r = k[A][B]2 overall order is 3
Calculate the unit of k
1. Rearrange rate equation to 2. Insert units and 3. Simplify fraction

give k as subject cancel
k= s-1
k = Rate k = mol dm-3s-1 Unit of k = mol-2dm6s-1
mol2dm-6
[A][B]2 mol dm-3.(moldm-3)2
Rate Equations
The rate equation relates mathematically the rate of reaction to the concentration of the reactants.
For the following reaction, aA + bB  r is used as symbol for rate

products, the generalised rate equation is: r = k[A]m[B]n
The unit of r is usually mol dm-3 s-1
The square brackets [A] means

m, n are called reaction orders the concentration of A
Orders are usually integers 0,1,2 (unit mol dm-3)
0 means the reaction is zero order with respect to that reactant k is called the rate constant
1 means first order
2 means second order
The total order for a reaction is worked
NOTE: the orders have nothing to do with the stoichiometric out by adding all the individual orders
coefficients in the balanced equation. They are worked out together (m+n)
experimentally
For zero order: the concentration of A has no effect on the

rate of reaction r = k[A]0 = k
For first order: the rate of reaction is directly proportional

to the concentration of A r = k[A]1
For second order: the rate of reaction is proportional to the

concentration of A squared r = k[A]2
The rate constant (k)
1. The units of k depend on the overall order of For a 1st order overall reaction the unit of k is
reaction. It must be worked out from the rate s-1
equation For a 2nd order overall reaction the unit of k is
2. The value of k is independent of concentration and mol-1dm3s-1
time. It is constant at a fixed temperature. For a 3rd order overall reaction the unit of k is
3. The value of k refers to a specific temperature and mol-2dm6s-1
it increases if we increase temperature
Example (first order overall)
Rate = k[A][B]0 m = 1 and n = 0 Remember: the values of the reaction orders must
- reaction is first order in A and zero order in B be determined from experiment; they cannot be
- overall order = 1 + 0 = 1 found by looking at the balanced reaction equation
- usually written: Rate = k[A]
Calculating units of k
1. Rearrange rate equation 2. Insert units and

to give k as subject cancel
k = Rate k = mol dm-3s-1

Unit of k = s-1
[A] mol dm-3
Example: Write rate equation for reaction between A and B
where A is 1st order and B is 2nd order.
r = k[A][B]2 overall order is 3
Calculate the unit of k
1. Rearrange rate equation to 2. Insert units and 3. Simplify fraction

give k as subject cancel
k= s-1
k = Rate k = mol dm-3s-1 Unit of k = mol-2dm6s-1
mol2dm-6
[A][B]2 mol dm-3.(moldm-3)2
Working out orders from experimental initial rate data
The initial rate is the rate at the start of the reaction, where it is fastest. It is
often obtained by taking the gradient of the conc vs time graph.
Normally to work out the rate equation we do a series of

experiments where the initial concentrations of reactants are
changed (one at a time) and measure the initial rate each time.
This data is normally presented in a table.
Example: work out the rate equation for the following reaction, A+ B+ 2C  D + 2E, using the initial rate
data in the table
Experiment [A] [B] [C] Rate In order to calculate the order for a particular
mol dm- mol dm-3 mol dm-3 mol dm-3 s-1 reactant it is easiest to compare two
3
experiments where only that reactant is
1 0.1 0.5 0.25 0.1 being changed
2 0.2 0.5 0.25 0.2
If conc is doubled and rate stays the same: order= 0
3 0.1 1.0 0.25 0.4
If conc is doubled and rate doubles: order= 1
4 0.1 0.5 0.5 0.1
If conc is doubled and rate quadruples : order= 2
For reactant A compare between experiments 1 and 2

For reactant A as the concentration doubles (B and C staying constant) so does the
rate. Therefore the order with respect to reactant A is first order
For reactant B compare between experiments 1 and 3 :

As the concentration of B doubles (A and C staying constant) the rate quadruples.
Therefore the order with respect to B is 2nd order
For reactant C compare between experiments 1 and 4 :

As the concentration of C doubles (A and B staying constant) the rate stays the same.
Therefore the order with respect to C is zero order
The reaction is 3rd order overall and the unit of the

The overall rate equation is r = k [A] [B]2
rate constant =mol-2dm6s-1
Working out orders when two reactant concentrations are changed simultaneously
In most questions it is possible to compare between two experiments where only one reactant has its initial
concentration changed. If, however, both reactants are changed then the effect of both individual changes on
concentration are multiplied together to give the effect on rate.
In a reaction where the rate equation is r = k [A] [B]2

If the [A] is x2 that rate would x2
If the [B] is x3 that rate would x32= x9
If these changes happened at the same time then the rate would x2x9= x 18
Example work out the rate equation for the reaction, between X and Y, using the initial rate data in the table
Experiment Initial concentration of Initial concentration Initial

X/ mol dm–3 of Y/ mol dm–3 rate/ mol dm–3 s–1
1 0.05 0.1 0.15 x 10–6
2 0.10 0.1 0.30 x 10–6
3 0.20 0.2 2.40 x 10–6
For reactant X compare between experiments 1 and 2

For reactant X as the concentration doubles (Y staying constant) so does the rate.
Therefore the order with respect to reactant X is first order
Comparing between experiments 2 and 3 :
Both X and Y double and the rate goes up by 8
We know X is first order so that will have doubled rate

The overall rate equation is r = k [X] [Y]2
The effect of Y, therefore, on rate is to have quadrupled it.
The reaction is 3rd order overall and the unit of
Y must be second order
the rate constant =mol-2dm6s-1
Calculating a value for k using initial rate data
Using the above example, choose any one of the experiments and put the values into the rate equation that
has been rearranged to give k. Using experiment 3:
r = k [X] [Y]2 k= r k = 2.40 x 10–6 k = 3.0 x 10-4 mol-2dm6s-1

[X] [Y]2
0.2 x 0.22
Remember k is the same for all experiments done at the same temperature.
Increasing the temperature increases the value of the rate constant k
6
Effect of Temperature on rate constant
Increasing the temperature increases the value of the

rate constant k
k
Increasing temperature increases the rate constant k. The
relationship is given by the Arrhenius equation k = Ae-Ea/RT
where A is a constant R is gas constant and Ea is activation
energy. temperature
The Arrhenius equation can be rearranged 1/T
ln (Rate)
ln k = constant – Ea/(RT)
k is proportional to the rate of reaction so ln k can be
replaced by ln(rate) Gradient = - Ea/ R
From plotting a graph of ln(rate) or ln k against 1/T the
activation energy can be calculated from measuring Ea = - gradient x R
the gradient of the line
1/T
Example
0.0029 0.003 0.0031 0.0032 0.0033 0.0034
Temperature time t -1.6
T (K) 1/T (s) 1/t Ln (1/t) x1,y1
297.3 0.003364 53 0.018868 -3.9703 -2.1
310.6 0.00322 24 0.041667 -3.1781
ln (Rate)
317.2 0.003153 16 0.0625 -2.7726 -2.6
323.9 0.003087 12 0.083333 -2.4849

-3.1
335.6 0.00298 6 0.166667 -1.7918
-3.6
x2,y2
gradient = y2-y1 The gradient should
x2-x1 always be -ve -4.1
In above example gradient =-5680 use a line of best fit

use all graph paper
Ea = - gradient x R (8.31) choose points far apart on the graph to
= - -5680 x8.31 calculate the gradient
= 47200 J mol-1
The unit of Ea using this equation will be J mol-1 .
Convert into kJ mol-1 by dividing 1000
Ea = +47.2 kJ mol-1
Rate Equations and mechanisms
A mechanism is a series of steps through which the reaction Each step can have a different rate of
progresses, often forming intermediate compounds. If all the reaction. The slowest step will control the
steps are added together they will add up to the overall overall rate of reaction. The slowest step
equation for the reaction is called the rate-determining step.
The molecularity (number of moles of each substance) of the molecules in the slowest
step will be the same as the order of reaction for each substance.
e.g. 0 moles of A in slow step would mean A is zero order.
1 mole of A in the slow step would mean A is first order
Example 2 overall reaction

Example 1 A + 2B + C  D + E
overall reaction Mechanism
A + 2B + C  D + E Step 1 A + B  X + D fast
Mechanism Step 2 X+CY slow
Step 1 A + B  X + D slow Step 3 Y+BE fast
Step 2 X+CY fast
Step 3 Y+BE fast r = k [X]1[C]1
r = k [A]1[B]1[C]o The intermediate X is not one of the reactants so
must be replaced with the substances that make
C is zero order as it appears in the up the intermediate in a previous step
mechanism in a fast step after the slow step A+BX+D
r = k[A]1[B]1[C]1
Investigating the rate of reaction between Iodine and propanone
Propanone reacts with iodine in acidic solution (the acid is a catalyst) as shown in the equation
below.
CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I–(aq)
This reaction can be followed by removing small samples from the reaction mixture with a
volumetric pipette. The sample is then quenched by adding excess sodium hydrogencarbonate to
neutralize acid catalyst which stops the reaction. Then the sample can be titrated with sodium
thiosulphate using a starch catalyst
2S2O32-(aq) + I2 (aq)  2I- (aq) + S4O62-(aq)

yellow/brown sol colourless sol
[I2] This reaction is zero order with respect to I2 but 1st order
with respect to the propanone and acid catalyst
The rate equation for the reaction is

Rate = k[CH3COCH3(aq)][H+(aq)]
If there is a zero order reactant there must

be at least two steps in the mechanism
because the rate determining step will not
involve the zero order reactant
Time (min)
The rate determining step of this reaction must therefore contain one propanone molecule and one H+ ion
forming an intermediate. The iodine will be involved in a subsequent faster step.
Example 3: SN1 or SN2?
Remember the nucleophilic substitution reaction of halogenoalkanes and hydroxide ions.

This is a one step mechanism
H CH3 H - H
δ+ δ-
H3C
-HO:
C Br  HO C Br
H3C C OH + :Br -
H
H H
CH3CH2Br + OH-  CH3CH2OH + Br- slow step

Primary halogenalkanes tend to
The rate equation is This is called SN2.
Substitution, Nucleophilic, react via the SN2 mechanism
r = k [CH3CH2Br] [OH-] 2 molecules in rate
determining step
SN1 nucleophilic substitution mechanism for tertiary halogenoalkanes
Tertiary halogenoalkanes
CH3 CH3 CH3 undergo this mechanism as the
+
tertiary carbocation is made
H3C C Br H3C C :OH- H3C C OH stabilised by the electron
releasing methyl groups around it.
CH3 CH3 CH3
(see alkenes topic for another
example of this).
The Br first breaks away The hydroxide
Also the bulky methyl groups
from the haloalkane to nucleophile then attacks
the positive carbon prevent the hydroxide ion from
form a carbocation attacking the halogenoalkane in
intermediate
the same way as the mechanism
above
Overall Reaction
The rate equation is This is called SN1.
(CH3)3CBr + OH–  (CH3)3COH + Br – Substitution, Nucleophilic,
r = k [(CH3)3CBr] 1 molecule in rate
Mechanism: determining step
(CH3)3CBr  (CH3)3C+ + Br – slow Primary halogenoalkanes don’t do the SN1 mechanism

because they would only form an unstable primary
(CH3)3C+ + OH–  (CH3)3COH fast
carbocation.
Example 4
Example 5
Overall Reaction
Using the rate equation rate = k[NO]2[H2] and
NO2(g) + CO(g)  NO(g) + CO2(g)
the overall equation 2NO(g) + 2H2(g) N2(g) + 2H2O(g), the
following three-step mechanism for the reaction was
Mechanism:
suggested. X and Y are intermediate species.
Step 1 NO2 + NO2 NO + NO3 slow
Step 1 NO + NO  X
Step 2 NO3 + CO  NO2 + CO2 fast
Step 2 X + H2 Y
• NO3 is a reaction intermediate
Step 3 Y + H2  N2 + 2H2O
NO2 appears twice in the slow steps so it
is second order. CO does not appear in Which one of the three steps is the rate-determining step?
the slow step so is zero order. Step 2 – as H2 appears in rate equation and
r=k [NO2]2 combination of step 1 and 2 is the ratio that
appears in the rate equation.
17. Organic Chemistry II
A2 Organic naming
Basic definitions
Hydrocarbon is a compound consisting of hydrogen and carbon only to know
Saturated: Contain single carbon-carbon bonds only Unsaturated : Contains a C=C double bond
Molecular formula: The formula which shows the actual number of each type of atom
Empirical formula: shows the simplest whole number ratio of atoms of each element in the compound
General formula: algebraic formula for a homologous series e.g. CnH2n
Displayed formula: shows all the covalent bonds present in a molecule
Homologous series are families of organic compounds with the same functional
group and same general formula.
•They show a gradual change in physical properties (e.g. boiling point).
• Each member differs by CH2 from the last.
• same chemical properties.
Functional group is an atom or group of atoms which when present in different molecules
causes them to have similar chemical properties.
Drawing Displayed formulae

Remember that the shape around the
H H H H carbon atom is tetrahedral and the bond
When drawing organic
angle is 109.5o
H C C C C H compounds add the
hydrogen atoms so that H H
H H H
H C H each carbon has 4 bonds
H C C H
H
General rules for naming carbon chains H H

Count the longest carbon chain and name appropriately code
no of
carbons
Find any branched chains and count how many carbons they contain meth 1
 Add the appropriate prefix for each branch chain eth 2
Eg -CH3 methyl or -C2H5 ethyl –C3H7 propyl prop 3
CH3 but 4
pent 5
2 CH2
hex 6
5
3,5-dimethylheptane hept 7
H3 C CH CH2 CH CH3
3
4 oct 8
CH2 6 non 9
CH3 7 dec 10
When compounds contain more than one functional group, the order of precedence determines which groups are
named with prefix or suffix forms. The highest precedence group takes the suffix, with all others taking the prefix
form. However, double and triple C-Cbonds only take suffix form.
Order of priority highest first:
Carboxylic acids >carboxylic acid derivative>nitriles>aldehydes>ketones>alcohols>amines
prefix / suffix
homologous functional group example
(* = usual use)
series
H H
alkenes C C suffix -ene C C ethene

H H
suffix* -ol H H H
alcohols C OH
prefix hydroxy-
H C C C O H Propan-1-ol
H H H
H H H
halogenoalkane C halogen
prefix chloro- H C C C Cl
bromo- 1-chloropropane
H H H
iodo-
O H O
suffix -al
aldehydes C H H C C H
prefix formyl- ethanal
H
H O H
O suffix* -one
ketones prefix oxo- H C C C H
C Propanone
H H
O H O
suffix -oic acid
carboxylic acids C OH H C C OH
Ethanoic acid
H
H H
suffix -nitrile
nitriles H C C C N
prefix cyano- Propanenitrile
C N
H H
suffix* -amine H H H
amines C NH2 prefix amino- Propylamine
H C C C NH2
Or propan-1-amine
H H H
H O H
O
esters H C C O C H Methyl ethanoate
C O
-yl –oate
H H
O
O
Acyl chloride CH 3 C ethanoylchloride
C -oyl chloride
Cl Cl
O
O
Amide
C -amide CH3 C ethanamide
NH2 NH2
General rules for naming functional groups
The functional group is indicated by a prefix or suffix. e.g. chloroethane
•When using a suffix, add in the following way :

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

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

methylpropane CHCl3 trichloromethane
however, if they are needed to
H H
avoid ambiguity. H C H
•The functional groups take precedence over branched 3-methylbut-1-ene is correct and not 2-methylbut-3-ene
chains in giving the lowest number
H H H H H
Where there are two or more of the same groups, di-, tri- or 2,3-dibromopentane.
H C C C C C H
tetra are used. Note the point made above about the addition of
H H Br H
‘e’ to the stem Br
Words are separated by numbers with dashes

CH2FCCl2CH2CH3 2,2-dichloro-1-fluorobutane.
 numbers are separated by commas
If there is more than one functional group or side chain, the 3-bromo-1-fluoropentane
CH2FCH2CHBrCH2CH3
groups are listed in alphabetical order (ignoring any di, tri).
The suffix for alkenes can go in front of other suffixes. CH2OHCHBrCH=CH2 2-bromobut-3-en-1-ol
Halogenoalkanes
H H Br H
Class the halogen as a substituent on the C chain and use the
H C C C C H 2-bromobutane
suffix -fluoro, -chloro, -bromo, or –iodo. (Give the position
number if necessary)
H H H H
Alcohols
OH
These have the ending -ol and if necessary the position
Butan-2-ol
number for the OH group is added between the name stem CH3 CH CH2 CH3
and the –ol 1 2 3 4
O
If the compound has an –OH group in addition to other H3C CH C 2-hydroxypropanoic acid
functional groups that need a suffix ending then the OH can be
named with the prefix hydroxy-): OH OH
HO CH2 CH2 OH Ethane-1,2-diol
If there are two or more -OH groups then di, tri are used. H2C OH
Add the ‘e’ on to the stem name though
propane-1,2,3-triol
HC OH
H2C OH
H
Aldehydes O
Ketones H O H
An aldehyde’s name ends in –al
It always has the C=O bond on the H C C
Ketones end in -one H C C C H
first carbon of the chain so it does
When ketones have 5C’s or more
not need an extra number. It is by H H
H
in a chain then it needs a number
default number one on the chain H Propanone
to show the position of the double
Ethanal bond. E.g. pentan-2-one
H O H O H
If two ketone groups then
Carboxylic acids H H di is put before –one and H C C C C C H
O
These have the ending -oic an an e is added to the H H H
acid but no number is stem
H C C C
necessary for the acid group Pentane-2,4-dione
as it must always be at the
end of the chain. The H H
O H O
The prefix oxo- should be
numbering always starts used for compounds that H3C C C
from the carboxylic acid end propanoic acid
contain a ketone group in O OH
addition to a carboxylic acid
If there are carboxylic acid groups on both ends of the or aldehyde 2-oxopropanoic acid
chain then it is called a - dioic acid
O O
Ethanedioic acid
C C
HO OH Note the e in this name
Nitriles H H H OH
These end in –nitrile, but the C of the H3C
CN group counts as the first carbon of H C C C CN C
the chain. Note the stem of the name is C
H3C N
different : butanenitrile and not H H H
butannitrile. butanenitrile 2-hydroxy-2-methylpropanenitrile
Carboxylic acid derivatives
Esters H
H H O
Esters have two parts to their names
H C C C O C H
The bit ending in –yl comes from the alcohol that has
formed it and is next to the single bonded oxygen.
H H H
The bit ending in –anoate comes from the carboxylic acid.
(This is the chain including the C=O bond) Methyl propanoate
Acyl Chlorides H3C O O

O O
add –oyl chloride to the stem CH3 C CH C C (CH2)3 C
name Cl
Cl H3C Cl Cl
ethanoyl chloride 2-methylpropanoyl chloride Pentanedioyl dichloride
Amides O Secondary and tertiary amides O

are named differently to show the
Add –amide to the stem CH3 C two (or three) carbon chains.
H3C CH2 C NH CH3
name NH2 The smaller alkyl group is
ethanamide preceded by an –N which plays N-methylpropanamide
the same role as a number in
positioning a side alkyl chain CH3 O CH3
O CH3
H3C CH C N CH3
H3C CH2 C N CH3 N,N,2-trimethylpropanamide
N,N-dimethylpropanamide
Isomers
Structural isomerism can arise from
Structural isomers: same molecular formula different
structures (or structural formulae)
•Chain isomerism
•Position isomerism
•Functional group isomerism
Chain isomers: Compounds with the same molecular formula but different structures of the carbon skeleton
H H H H H
H H H H H
H C C C C H H C H
H C C C C C H H H
H H H
H C H H C C C H
H H H H H
H H
H H C H
pentane
2-methylbutane H
2,2-dimethylpropane
position isomers: Compounds with the same molecular formula but different structures due to
different positions of the same functional group on the same carbon skeleton
H H H H H H
H C C C H 1-bromopropane H C C C H 2-bromopropane
Br H H H Br H
Functional group isomers: Compounds with the same molecular formula but with atoms arranges to give different
functional groups
H H H H
H C O C H Methoxymethane: an ether
H C C O H
ethanol: an alcohol
H H
H H
H H
H H
C
H C C H
Cyclohexane- cyclo alkane CH3CH2CH2CH2CH=CH2 hexene- alkene

H C C H
C
H H
H H
Aldehydes and ketones of the same chain length would be classed as functional
group isomers- e.g. Propanal and propanone (both C3H6O)
Stereoisomerism
Definition: Stereoisomers have the same structural formulae There are two types of stereoisomerism:
but have a different spatial arrangement of atoms geometrical (E- Z isomerism) and optical
isomerism
Alkenes can exhibit a type of isomerism called E-Z stereoisomerism
E-Z isomers exist due to restricted

rotation about the C=C bond
Single carbon-carbon covalent

bonds can easily rotate
E-Z stereoisomers arise when:

(a) There is restricted rotation around the C=C double bond.
(b) There are two different groups/atoms attached both ends of
the restricted double bond
H H
two different groups H H
H C C H attached either end of
the restricted double H C C H But-1-ene
C C
bond- leads to EZ C C
H H H H isomers H H
H H
two identical groups attached to
Z- but-2-ene
one end of the restricted double
H
H These are two bond – no E-Z isomers
C H isomers as the lack
H of rotation around But-1-ene is a structural isomer of But-2-
C C the double bonds
H ene but does not show E-Z isomerism
means one cannot
H C
H
be switched to the Naming E-Z stereoisomers
H other
On both sides of the double bond determine the
E -but-2-ene priority group
PRIORITY Group: The atom with the bigger
Ar is classed as the priority atom
Priority Priority
Cl Cl Cl H
group group
side 1 side 2
C C C C
Z-1,2-dichloroethene
H H E-1,2-dichloroethene
H Cl
If the priority atom is on the same side of the If the priority atom is on the opposite side of
double bond it is labelled Z from the german the double bond it is labelled E from the
zusammen (The Zame Zide!) german entgegen (The Epposite side!)
17A Optical Isomerism

A carbon atom that has
Optical isomerism occurs in carbon compounds with 4 H H H H
four different groups
different groups of atoms attached to a carbon (called
attached is called a chiral
an asymmetric carbon). H C C C C H
(asymmetric) carbon
H H O H atom
These four groups are arranged H
tetrahedrally around the carbon.
OH OH This causes two

A mixture containing a 50/50 mixture of the
different isomers that
C C two isomers (enantiomers) is described as
are not superimposable
CH3 H3C being a racemate or racemic mixture.
H5 C2 C2 H5 to be formed. They are
H H mirror images
Many naturally occurring molecules
contain chiral C atoms, but are usually
Two compounds that are optical isomers of
found in nature as a pure enantiomer
each other are called enantiomers.
Different systems of nomenclature are is
Optical isomers have similar physical and chemical properties, existence for optical isomers. D/L or +/- are
but they rotate plane polarised light in different directions. commonly used, but both have been
superseded by the more useful and informative
One enantiomer rotates it in one direction and the other enantiomer R/S system (this is not on the syllabus – for
rotates it by the same amount in the opposite direction. information only).
One optical isomer will rotate light clockwise (+)(called

dextrorotatory). The other will rotate it anticlockwise(-)(called
laevorotatory).
Racemate
A racemic mixture (a mixture of equal amounts of the two -ve enantiomer +ve enantiomer
no rotation
optical isomers) will not rotate plane-polarised light. Anticlockwise clockwise
rotation rotation
Chemical Reactions and Optical Isomers
Formation of a racemate
CH3
A racemate will be formed in a reaction H
mechanism when a trigonal planar reactant or C
intermediate is approached from both sides by NC:
:CN
an attacking species
O
Nucleophilic addition of HCN to aldehydes
H
and ketones (unsymmetrical) when the H H3 C CN
trigonal planar carbonyl is approached from NC CH3
both sides by the HCN attacking species: There is an equal chance of C
C
results in the formation of a racemate either enantiomer forming so
a racemate forms. No
OH OH
optical activity is seen
Formation of a racemate with SN1 mechanism H
Br CH C
H3C + CH2 3
H3C C CH2 CH3 C H3C C2H5
H H :OH- OH
H
The Br first breaks Because a
The OH- ion can then attack C racemate forms
away from the
from either side resulting in there will be no
haloalkane to form a H5C2 CH3
different enantiomers and a optical activity in
planar carbocation
racemate forms HO the products
intermediate
Comparison with SN2 mechanism

In the SN2 mechanism no intermediates are formed and the reaction occurs via a transition state.
-
CH3 H
Br OH
H3C C CH2 CH3 HO C Br H3C C CH2 CH3
H :OH- CH 2CH 3 H
If the reactant was chiral then during the reaction the opposite enantiomer would form.
The product will rotate light in the opposite direction to the reactant
A racemate can also be formed in the AS reaction of the

electrophilic addition of HBr to an unsymmetrical alkene
:Br - H
H The bromide can H
+ attack this planar
δ+ δ- C CH2 carbocation from C
C
H Br both sides leading to CH2 Br CH2
H3C CH3 a racemate H3C Br
CH3 CH3
CH3
H2C CH CH2 CH3
:Br - Major product s 90%
If the alkene is H H
unsymmetrical, addition of +
hydrogen bromide can C C CH2 CH3
CH2 CH2 CH2 CH3 Minor
lead to isomeric products. H product
H
Br 10%
Compounds with C=O group
Carbonyls are compounds with a C=O bond.
17B Carbonyls: Aldehydes and Ketones They can be either aldehydes or ketones
H O H O H If the C=O is in the middle of

If the C=O is on the end of the
H. C C chain with an H attached it is an H C C C H the chain it is a ketone
The name will end in -one
aldehyde. H H
H H The name will end in –al
CH3COCH3 propanone
CH3CHO ethanal
Solubility in water
CH3
The smaller carbonyls are soluble Pure carbonyls cannot hydrogen bond, but
in water because they can form O H O C bond instead by permanent dipole bonding.
hydrogen bonds with water.
H CH3
δ-
Reactions of carbonyls O
In comparison to the C=C bond in
The C=O bond is polarised because alkenes, the C=O is stronger and does
O is more electronegative than δ+ not undergo addition reactions easily.
C
carbon. The positive carbon atom
attracts nucleophiles. H3C CH3
This is in contrast to the electrophiles
that are attracted to the C=C .
nucleophile
Oxidation Reactions
Potassium dichromate K2Cr2O7 is Key point: Aldehydes

Primary alcohol  aldehydes  carboxylic acid
an oxidising agent that causes can be oxidised to
alcohols and aldehydes to Secondary alcohol  ketones carboxylic acids, but
oxidise. Tertiary alcohols do not oxidise ketones cannot be
oxidised.
Oxidation of Aldehydes
Reaction: aldehyde  carboxylic acid H H O H H O

Reagent: potassium dichromate (VI) solution and H C C C + [O]  H C C C
dilute sulphuric acid.
Conditions: heat under reflux H H H H H O H
Full Equation for oxidation RCHO + [O]  RCO2H

3CH3CHO + Cr2O72- + 8H+  3 CH3CO2H + 4H2O + 2Cr3+
Aldehydes can also be oxidised using Fehling’s
Observation: the orange dichromate ion solution or Tollen’s Reagent. These are used
(Cr2O72-) reduces to the green Cr 3+ ion as tests for the presence of aldehyde groups
Tollen’s Reagent
Fehling’s solution
Reagent: Tollen’s Reagent formed by mixing
aqueous ammonia and silver nitrate. The
active substance is the complex ion of Reagent: Fehling’s Solution containing blue Cu 2+ ions.
[Ag(NH3)2]+ . Conditions: heat gently
Conditions: heat gently Reaction: aldehydes only are oxidised by Fehling’s
Solution into a carboxylic acid and the copper ions
Reaction: aldehydes only are oxidised by are reduced to copper(I) oxide . .
Tollen’s reagent into a carboxylic acid and Observation: Aldehydes :Blue Cu 2+ ions in solution
the silver(I) ions are reduced to silver atoms change to a red precipitate of Cu 2O. Ketones do
Observation: with aldehydes, a silver mirror forms not react.
coating the inside of the test tube. Ketones
result in no change. CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+
CH3CHO + 2Ag+ + H2O  CH3COOH + 2Ag + 2H+

8
Reduction of carbonyls Reducing agents such as NaBH4 (sodium tetrahydridoborate)
Reagents: LiAlH4 In dry ether or LiAlH4 (lithium tetrahydridoaluminate) will reduce carbonyls
Conditions: Room temperature and pressure to alcohols.
Type of reaction: Reduction
Role of reagent: Reducing agent
Aldehydes will be reduced to primary alcohols Ketones will be reduced to secondary alcohols.
H H O H H H H O H H H H
H C C C + 2[H] H C C C O H H C C C H + 2[H]  H C C C H
H H H H H H H O H
H H
propanal Propan-1-ol propanone H
Propan-2-ol
Addition of hydrogen cyanide to carbonyls to form hydroxynitriles

R
Reaction: carbonyl  hydroxynitrile
When naming hydroxy
Reagent: HCN in presence of KCN NC C OH
nitriles the CN becomes
Conditions: Room temperature and pressure
part of the main chain
Mechanism: nucleophilic addition
H
hydroxynitrile
CH3COCH3+ HCN  CH3C(OH)(CN)CH3 CH3
NC C OH
2-hydroxy-2-methylpropanenitrile The extra KCN increases the
CH3 concentration of the CN- ion
CH3
CH3CHO + HCN  CH3CH(OH)CN nucleophile needed for the
NC C OH first step of the mechanism
2-hydroxypropanenitrile H
Nucleophilic Addition Mechanism

δ-
O
O:
- -
H CN O H
δ+ H3C C CH3
C H3C C CH3
H3C CH3
CN CN
:CN-
Reaction of carbonyls with iodine in presence of alkali
Reagents: Iodine and sodium hydroxide Only carbonyls with a methyl group next to O
Conditions: warm very gently the C=O bond will do this reaction. Ethanal
is the only aldehyde that reacts. More H3C C H
The product CHI3 is a yellow crystalline commonly is methyl ketones.
precipitate with an antiseptic smell
This reaction is called the Iodoform test
CH3COCH3 + 3I2 + 4NaOH → CHI3 + CH3COONa + 3NaI +3H2O
CH3COCH2CH3+ 3I2 + 4NaOH → CHI3 + CH3CH2COONa + 3NaI +3H2O
Reaction with 2,4-dinitro phenylhydrazine
2,4-DNP reacts with both aldehydes and ketones. The Use 2,4-DNP to identify if the compound is a
product is an orange precipitate, It can be used as a test carbonyl. Then to differentiate an aldehyde
for a carbonyl group in a compound. from a ketone use Tollen’s reagent.
The melting point of the crystal formed can be used to help identify which carbonyl was used. Take the melting
point of orange crystals product from 2,4-DNP. Compare melting point with known values in database
H O 2N You don’t need to

learn these equations
H3C C
..
H2N NH NO2
for the exam
+
O 2,4-DNP
addition
O 2N H O 2N
H
elimination of
water
H3C C NH NH NO2 H3C C N NH NO2
orange precipitate
OH
17C Carboxylic Acids

Solubility in Water

Acidity The smaller carboxylic (up to C4) H
 
The carboxylic acid are only weak acids acids dissolve in water in all O H O
in water and only slightly dissociate, but proportions but after this the solubility 
H3C C
they are strong enough to displace rapidly reduces. They dissolve   H
carbon dioxide from carbonates. because they can hydrogen bond to 
O H O
the water molecules.
H
CH3CO2H(aq) CH3CO2-(aq)+ H+(aq)
Hydrogen bonding in solid ethanoic acid

δ- Hydrogen bonding
δ - between dimer in
δ+
solid ethanoic acid
O H O
C CH3
H3C C δ -
Solid Ethanoic
δ- δ+
O H O appears to have Mr
of 120
Delocalisation
The delocalised ion has equal C-O bond lengths. If
The carboxylic acid salts are stabilised by delocalisation, delocalisation did not occur, the C=O bond would be
which makes the dissociation more likely. shorter than the C-O bond.
O O The pi charge cloud has O

delocalised H3C C delocalised and spread out. The
H3C C delocalisation makes the ion C
H3C
OH O more stable and therefore more
likely to form.
O
Strength of carboxylic acids
O O Increasing chain length pushes

delocalised electron density on to the COO-
H3C CH2 C H3C CH2 C
ion, making it more negative and
OH O less stable. This make the acid
less strong.
Alkyl groups electron releasing
Propanoic acid less acidic than ethanoic acid
Cl O Cl O Electronegative chlorine atoms

H C C delocalised withdraw electron density from
H C C the COO- ion, making it less
OH negative and more stable. This
H O
H make the acid more strong.
Chlorine electron withdrawing
chloroethanoic acid more acidic than ethanoic acid
Methods of preparing carboxylic acids

Full Oxidation of Primary Alcohols
Reaction: primary alcohol  carboxylic acid Observation: the

Reagent: potassium dichromate(VI) solution and dilute sulphuric acid orange dichromate
Conditions: use an excess of dichromate, and heat under reflux: (distill off ion (Cr2O72-) reduces
product after the reaction has finished) to the green Cr 3+ ion
H H H H H
O
H C C C O H + 2 [O] H C C C + H2O
H H H O H
H H
CH3CH2CH2OH + 2[O]  CH3CH2COOH + H2O

propan-1-ol Propanoic acid
Oxidation of Aldehydes
Reaction: aldehyde  carboxylic acid H H O H H O

Reagent: potassium dichromate (VI) solution and H C C C + [O]  H C C C
Conditions: heat under reflux H H H H H O H
Full Equation for oxidation RCHO + [O]  RCOOH

3CH3CHO + Cr2O72- + 8H+  3 CH3COOH + 4H2O + 2Cr3+
Hydrolysis of Nitriles
Reaction: Nitrile  carboxylic acid
Reagent: dilute hydrochloric/ sulphuric acid.
Conditions: heat under reflux
CH3CH2CN + H+ + 2H2O  CH3CH2COOH + NH4+
The Reactions of Carboxylic Acids
Reduction of carboxylic acids to alcohols

Lithium tetrahydridoaluminate (LiAlH4) is a
Carboxylic acids will be reduced to primary alcohols
strong reducing agent
H H O H H H
Reagents: LiAlH4 In dry ether
Conditions: Room temperature and pressure H C C C + 4[H] H C C C O H + H2O
Type of reaction: Reduction H H O H H H H

Propanoic acid Propan-1-ol
Role of reagent: Reducing agent
Salt formation reactions of carboxylic acids

Carboxylic acids can form salts with metals, alkalis and
carbonates.
acid + metal (Na)  salt + hydrogen The effervescence caused by production of CO2
2CH3CO2H + 2Na  2CH3CO2-Na+ + H2 with carboxylic acids with solid Na2CO3 or
aqueous NaHCO3 can be used as a functional
acid + alkali (NaOH)  salt + water group test for carboxylic acids
CH3CO2H + NaOH  CH3CO2-Na+ + H2O
acid + carbonate (Na2CO3)  salt + water + CO2

2CH3CO2H + Na2CO3  2CH3CO2-Na+ + H2O + CO2
Oxidation of methanoic acid O O It forms carbonic acid

Carboxylic acids cannot be oxidised by using (H2 CO3 ) which can
oxidising agents but methanoic acid is an H C + [O]  H O C decompose to give
exception as its structure has effectively an O H O H CO2
aldehyde group
Reaction of carboxylic acid with phosphorous (V) chloride
Reaction: carboxylic acid  acyl chloride This reaction with PCl5 (phosphorous(v)chloride)
Reagent: PCl5 phosphorous(v)chloride can be used as a test for carboxylic acids. You would
Conditions: room temp observe misty fumes of HCl produced.
CH3COOH + PCl5  CH3COCl + POCl3 + HCl
O O
+ PCl5  + POCl3 + HCl
H3C C H3C C
OH Cl
Esterification
H H O H Esters have two parts
Carboxylic acids react with alcohols, in the to their names, eg
presence of a strong acid catalyst, to form H C C C O C H methyl propanoate.
esters and water. H H H
H+ The bit ending in –anoate The bit ending in –yl comes from
Carboxylic Acid + Alcohol Ester + water comes from the carboxylic the alcohol that has formed it
acid and includes the C in and is next to the single bonded
the C=O bond. oxygen.
H H H O H H
O The reaction is reversible. The
H+ reaction is quite slow and needs
+ H C C O H H C C O C C H + H2O
H3C C heating under reflux, (often for
OH H H H H H several hours or days). Low yields
(50% ish) are achieved. An acid
CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O catalyst (H2SO4) is needed.
Ethanoic acid Ethanol Ethyl Ethanoate
Uses of Esters
Esters can have pleasant smells
Esters are sweet smelling
For use in perfumes they need to be non toxic, soluble in solvent such as
compounds that can be used in
ethanol, volatile (turns into gas easily), and not react with water.
perfumes and flavourings.
Esters can be used as solvents Although polar, they do not form hydrogen bonds (reason: there is no
for polar organic substances hydrogen bonded to a highly electronegative atom)
thus, they have much lower b.p. than the hydrogen-bonded carboxylic
Ethyl ethanoate is used as a acids they came from. They are also almost insoluble in water
solvent in glues and printing inks
Hydrolysis of esters Esters can be hydrolysed and split up by either heating with acid or with sodium hydroxide.
i) with acid
This reaction is the reverse reaction of ester formation. When an
reagents: dilute acid (HCl)
ester is hydrolysed a carboxylic acid and an alcohol are formed.
conditions: heat under reflux
H+
This reaction is reversible and does
CH3CH2CO2CH2CH3 + H2O CH3CH2CO2H + CH3CH2OH
not give a good yield of the products.
ethyl propanoate
ii) with sodium hydroxide

reagents: dilute sodium hydroxide CH3CH2CO2CH3 + NaOH  CH3CH2CO2- Na+ + CH3OH
conditions: heat under reflux methyl propanoate sodium propanoate methanol
The carboxylic acid salt product is the anion of the carboxylic acid.
This reaction goes to completion. The anion is resistant to attack by weak nucleophiles such as alcohols,
so the reaction is not reversible.
13
Carboxylic acid derivatives: Acyl Chlorides
Acyl Chlorides
O Acyl chlorides are The Cl group is classed as a good leaving
much more reactive groups (to do with less effective delocalisation.)
CH3 C
than carboxylic acids This makes acyl chlorides and acid anhydrides
Cl much more reactive than carboxylic acids and
ethanoyl chloride esters
Reaction with water Reaction with alcohol
Change in functional group: acyl chloride  Change in functional group: acyl chloride  ester
carboxylic acid Reagent: alcohol
Reagent: water Conditions: room temp.
Conditions: room temp.
RCOCl (l) + CH3CH2OH  RCO2CH2CH3 + HCl (g)
RCOCl (l) + H2O  RCO2H + HCl (g)
O H O H H
O O CH 3 C + CH3CH2OH  H C C O C C H + HCl
CH3 C + H2O  CH3 C + HCl (g) Cl H H H
Cl OH
Observation: Steamy white fumes of HCl are
Observation: Steamy white fumes of HCl
given off
are given off
This reaction for making esters is much better than using

carboxylic acids as the reaction is much quicker and it is
not a reversible reaction
Reaction with ammonia Reaction with primary amines

Change in functional group: acyl chloride 
primary amide
secondary amide
Reagent: ammonia
Reagent: primary amine
RCOCl (l) +2NH3  RCONH2 + NH4Cl (s) RCOCl +2CH3NH2  RCONHCH3 + CH3NH3+Cl-
O O
O
O + CH3NH3+Cl-
CH3 C + 2NH3  CH3 C + NH4Cl (s) CH3 C + 2CH3NH2  CH3 C NH CH3
Cl NH2
Cl
N-methylethanamide
Observation: white smoke of NH4Cl is given off
Polyesters
There are two types of polymerisation: addition and condensation
Condensation Polymerisation
In condensation polymerisation there are two different monomers
The two most common types of that add together and a small molecule is usually given off as a
condensation polymers are side-product e.g. H2O or HCl.
polyesters and polyamides which
involve the formation of an ester The monomers usually have the same functional group on both ends
linkage or an amide linkage. of the molecule e.g. di-amine, di carboxylic acid, diol, diacyl chloride.
Forming polyesters uses these reactions we met earlier in the course
Carboxylic Acid + Alcohol  Ester + water Acyl chloride + Alcohol  Ester + HCl
If we have the same functional group on each end of molecule we can make polymers so we have the
analogous equations:
dicarboxylic acid + diol  poly(ester) + water diacyl dichloride + diol  poly(ester) + HCl
Using the carboxylic acid to make the ester or amide would need an acid catalyst and would only give an
equilibrium mixture. The more reactive acyl chloride goes to completion and does not need a catalyst but does
produce hazardous HCl fumes.
Terylene- a common polyester

O O
O O
n + n HO CH CH OH C C O CH2 CH2 O + 2n-1 H2O
C C 2 2
n
HO OH Ethane-1,2-diol
The -1 here is because at
Benzene-1,4-dicarboxylic acid
each end of the chain the H
Terylene fabric is used in clothing, tire cords and OH are still present
O O O O
n C (CH2)3 C + n HO OH + 2n-1 HCl
C (CH2)3 C O O
Cl Cl n
Pentanedioyl dichloride Benzene-1,4-diol
It is also possible for polyamides and polyesters to form from one monomer, if that monomer
contains both the functional groups needed to react
3 repeating units
H O H O H O
HO O
CH C HO C C O C C O C C OH
H 3C OH CH3 CH3 CH3

2-hydroxypropanoic acid (lactic acid) 3 repeating units poly(lactic acid)
OH
O O
O
OH 1 repeating unit
4-hydroxypentanoic acid
O
O
It is possible for some of these compounds to form O
O O various cyclic esters under different conditions from
forming the polymer.
You do not need to learn these but may be asked to
O deduce structures from information given
Chemical reactivity of condensation polymers

The reactivity can be explained by the presence of
polyesters can be broken down by hydrolysis and polar bonds which can attract attacking species
are, therefore, biodegradable such as nucleophiles and acids
Polyesters can be hydrolysed by acid and alkali

With HCl a polyester will be hydrolysed and split up in to the original dicarboxylic acid and diol
With NaOH an polyester will be hydrolysed and split up into the diol and dicarboxylic acid salt.
18: Organic Chemistry III
18A. Arenes
All of the organic substances we have
There are two major classes of organic chemicals
looked at so far have been aliphatic
aliphatic : straight or branched chain organic substances
aromatic or arene: includes one or more ring of six carbon Benzene belongs to the aromatic class.
atoms with delocalised bonding.
Benzene’s Structure In 1865 Kekule suggested the following

The simplest arene is benzene. It has the molecular formula C6H6 structure for Benzene consisting of
Its basic structure is six C atoms in a hexagonal ring, with one H alternate single and double covalent
atom bonded to each C atom bonds between the carbon atoms
Each C atom is bonded to two other C atoms and one H atom by H
single covalent σ-bonds. This leaves one unused electron on each
C atom in a p orbital, perpendicular to the plane of the ring. H C H
The Six p electrons are delocalised in a ring structure above and C C
below the plane of carbon atoms
C C
H C H
H H H H
H
H H H H
This structure is not correct. Evidence
suggests that all the C-C bonds are the
H H H H
same length.
In formulae we draw a circle to show

this delocalised system The six electrons in the pi bonds are delocalised and spread out
over the whole ring. Delocalised means not attached to a particular
atom.
Benzene is a planar molecule.The evidence suggests all the C-C

Abbreviated bonds are the same and have a length and bond energy between a
formula C-C single and C=C double bond
Displayed formula The H-C-C bond angle is 120o in Benzene
Enthalpies of Hydrogenation
Theoretically because there
+ H2  H = -120 kJ/mol are 3 double bonds one might
enthalpy
expect the amount of energy H = -152kJ/mol

cyclohexene cyclohexane x3 to be 3 times as much. delocalisation
energy
-360 kJ/mol
+ 3H2  H = -360 kJ/mol Theoretical
However, the real amount of value
Non delocalised energy is less. The 6 pi
structure electrons are delocalised and H = -208kJ/mol
not arranged in 3 double bonds actual value
+ 3H2  H = -208kJ/mol
This when represented on an energy level
delocalised diagram shows that the delocalised benzene
structure is more thermodynamically stable.
The increase in stability connected to delocalisation is called

the delocalisation energy
Reactions of Benzene
Benzene does not generally undergo addition reactions because these would involve breaking up the delocalised
system. Most of Benzene’s reactions involve substituting one H for another atom or group of atoms. Benzene has
a high electron density and so attracts electrophiles. It reactions are usually electrophilic substitutions
Naming aromatic molecules
Naming aromatic compounds can be complicated. The simplest molecules are derivatives of benzene and have
benzene at the root of the name
CH3 C2H5 Cl Br NO 2 CO2H CHO
Methylbenzene ethylbenzene chlorobenzene bromobenzene nitrobenzene benzenecarboxylic benzaldehyde

acid
If two or more substituents are present on the benzene ring, their positions must be indicated by the use of
numbers. This should be done to give the lowest possible numbers to the substituents. When two or more
different substituents are present, they are listed in alphabetical order and di, tri prefixes should be used.
CH3 CH3
CH3
COOH
O 2N NO2
CH3
Cl NO2
OH
1,3-dimethylbenzene
1-chloro- 4-methylbenzene 4-hydroxybenzenecarboxylic acid 2,4,6-trinitromethylbenzene
In other molecules the benzene ring can be regarded as a substituent side group on another molecule, like
alkyl groups are. The C6H5- group is known as the phenyl group.
O
NH2 CH CH2 CH3
H3C CH CH2 CH3 O
C
H3C C O
phenylamine phenylethene
2-phenylbutane
phenylethanone phenylethanoate
Toxicity of Benzene
Benzene is a carcinogen (cancers causing molecule) and is banned for use in schools.
Methylbenzene is less toxic and also reacts more readily than benzene as the methyl side group releases
electrons into the delocalised system making it more attractive to electrophiles
Reactions of Benzene
Combustion
Benzene will combust with a very sooty flame.
Benzene + oxygen  carbon dioxide + water The lower the carbon to hydrogen ratio the
C6H6 (l) + 7.5 O2  6 CO2 + 3 H20 sootier the flame.
Halogenation of Benzene
Change in functional group: benzene  Bromobenzene This reaction can be done with chlorine.
Reagents: Bromine The catalyst can be AlCl3 or FeCl3
Conditions: iron(III) bromide catalyst FeBr3
It is possible to create the iron(III)
Mechanism: Electrophillic Substitution
bromide in situ by reacting iron with
bromine
Overall Equation for reaction Br
Equation for Formation of electrophiles:
+ HBr (Learn!)
+ Br2  AlCl3 + Cl2  AlCl4– + Cl+
FeBr3 + Br2  FeBr4– + Br+
Mechanism Cl
Cl+
H Cl
+
The H+ ion reacts with the AlCl4- to H+ + AlCl4-  AlCl3 + HCl

reform AlCl3 catalyst and HCl.
Nitration of Benzene
Change in functional group: benzene  nitrobenzene
Reagents: conc nitric acid in the presence of concentrated Importance of this reaction
sulphuric acid (catalyst) Nitration of benzene and other arenes is
Mechanism: Electrophilic Substitution an important step in synthesising useful
Electrophile: NO2+ compounds
e.g. explosive manufacture (like TNT,
Overall Equation for reaction trinitrotoluene/ 2,4,6-
NO2
trinitromethylbenzene)
+ NO2 +  + H+ and formation of amines from which
dyestuffs are manufactured. (The reaction
for this is covered in the amines section.)
Equation for Formation of electrophile: (Learn!)
HNO3 + 2H2SO4  NO2+ + 2HSO4- + H3O+
Mechanism This reaction is done at 60oC.

NO 2 On using higher temperatures
HSO4-
NO2+ NO 2 a second nitro group can be
H substituted onto different
+ positions on the ring
If the benzene ring already has

The horseshoe shape of the a side group e.g. methyl then
intermediate must not extend the Nitro group can also join on
beyond C’s 2 to 6 different positions. A-level does
not require knowledge of what
The H+ ion rejoins with the HSO4- to H+ + HSO4-  H2SO4 positions the groups go on.
reform H2SO4 catalyst.
3
Hydrogenation of Benzene
Reaction: benzene  cyclohexane Ni

Reagents: Hydrogen Catalyst
+ 3H2
Conditons: Nickel catalyst at 200C and 30 atm
Type of reaction: Addition and reduction
Friedel Crafts Alkylation
Change in functional group: benzene  alkylbenzene

Reagents: chloroalkane in the presence of anhydrous Any chloroalkane can be used RCl where
aluminium chloride catalyst R is any alkyl group Eg –CH3 , -C2H5.
Conditions: heat under reflux The electrophile is the R+.
Mechanism: Electrophilic Substitution
Formation of the electrophile.

AlCl3 + CH3CH2Cl  CH3CH2+ AlCl4-
Overall Equation for reaction

CH2CH3
CH3CH2+ AlCl4- + + AlCl3 + HCl
ethylbenzene
Mechanism
+CH CH
2 3 CH 2CH 3
CH2CH3
H
+
The H+ ion reacts with the AlCl4- to

H+ + AlCl4-  AlCl3 + HCl
Friedel Crafts Acylation
Change in functional group: benzene  phenyl ketone
Reagents: acyl chloride in the presence of anhydrous Any acyl chloride can be used RCOCl where
aluminium chloride catalyst R is any alkyl group e.g. –CH3 , -C2H5. The
Conditions: heat under reflux (50OC) electrophile is the RCO+.
Mechanism: Electrophilic Substitution
Equation for Formation of the electrophile.

AlCl3 + CH3COCl  CH3CO+ AlCl4-
Overall Equation for reaction These are important

O
reactions in organic
C synthesis because they
CH3CO+ AlCl4- + CH3 + AlCl3 + HCl introduce a reactive
functional group on to the
benzene ring
phenylethanone
Mechanism O O
+ O
C CH3 C CH3
C
CH3
H
+
The H+ ion reacts with the AlCl4- to
H+ + AlCl4-  AlCl3 + HCl
Effect of side groups on benzene ring
Electron releasing side groups such as alkyl groups, phenols and amines releases electrons into the
delocalised system making a higher electron density in the ring and it more attractive to electrophiles.
They will therefore carry out the substitution reactions more readily with milder conditions
Effect of delocalisation on side groups with lone pairs
If a –OH group, a Cl atom or an NH2 group is directly attached to a benzene ring the
delocalisation in the benzene ring will extend to include the lone pairs on the N,O and Cl. This
changes the properties and reactions of the side group
Cl NH2
OH
chlorobenzene
phenylamine
phenol
The C-Cl bond is made stronger.
Typical halogenoalkane Delocalisation makes the C-O Less basic than aliphatic
substitution and elimination bond stronger and the O-H bond amines as lone pair is
reactions do not occur. Also the weaker. Phenol does not act like delocalised and less
electron rich benzene ring will an alcohol- it is more acidic and available for accepting a
repel nucleophiles does not oxidise proton
Phenols
In a phenol the OH group is directly attached to the CH2OH

benzene ring.
OH
In a phenol the lone pair of electrons on the
oxygen is delocalised with the electron
charge cloud of the arene ring.
The delocalised bonding changes the
This is not a phenol, but is
reactivity of the OH group and the arene ring.
an alcohol because the
OH group is attached to an
alkyl group rather than the
Phenols are very weakly acidic. They are weaker acids than carboxylic acids. benzene ring.
Both phenols and carboxylic acids will react with sodium metal and sodium
hydroxide. Only carboxylic acids will react with sodium carbonate as a phenol
is not strong enough an acid to react.
-
OH + Na O Na+ + ½ H2
The sodium phenoxide

- compound is more soluble
OH + NaOH O Na+ + H2O
than the original phenol. So
the solid phenol dissolves on
sodium phenoxide addition of NaOH
Reaction of phenol with Bromine
Reagents: Bromine water

Conditions: room temp
OH Phenol does not need a FeBr3
OH
catalyst like benzene and
Br Br undergoes multiple
substitution whereas benzene
+ 3 Br2 + 3 HBr will only add one Br.
The product in this reaction is a

Br white solid
2,4,6 –tribromophenol
In phenol the lone pair of electrons on the oxygen (p- orbital) is

partially delocalised into the ring. The electron density increases
and the Br2 is more polarised
Phenols are used in the production of plastics,

antiseptics, disinfectants and resins for paints.
18B. Amines, Amides and Amino Acids
Naming
H H H
Amines H2N O
These end in –amine. H C C C NH2 If there is another
There is, however, rather confusingly CH C
priority functional group
two ways of using this suffix. H H H
as well as the amine H3C O H
The exam board tend to use the propylamine group then the prefix
common version where the name Or propan-1-amine 2-aminopropanoic acid.
amino is used.
stem ends in -yl propylamine.
The IUPAC version of the same
chemical is propan-1-amine. (This is
used in the same way as naming
alcohols)
If the amine is secondary and has two alkyl CH3CH2CH2NHCH3

groups attached to the nitrogen, then each N-methylpropylamine (common name)
chain is named and the smaller alkyl group N-methylpropan-1-amine (IUPAC name)
is preceded by an –N which plays the same
role as a number in positioning a side alkyl CH2 CH2
chain H3C NH CH3
Diethylamine (common name- does not use N if

In the common naming version if the chains are same length)
chain lengths are the same an –N is N-ethylethanamine (IUPAC name does still use N)
not used
CH3CH2 CH2 N CH3

If a tertiary amine similar rules apply,
and each alkyl side group is given an CH3
N N,N-dimethylpropylamine (common name)
N,N-dimethylpropan-1-amine (IUPAC name)
H H
N (CH2)6 N It could also be named
1,6-diaminohexane
H H
hexane-1,6-diamine
Amides
O Secondary and tertiary amides

Add –amide to the stem are named differently to show the O
name CH3 C two (or three) carbon chains.
NH2 The smaller alkyl group is
preceded by an –N which plays H3C CH2 C NH CH3
ethanamide the same role as a number in
N-methylpropanamide
positioning a side alkyl chain
O CH3
CH3 O CH3
H3C CH2 C N CH3
H3C CH C N CH3
N,N-dimethylpropanamide N,N,2-trimethylpropanamide
Properties of Amines
Amines have a characteristic fishy smell H δ+
δ- δ+ δ-
Small amines can form hydrogen bonds with water

CH3 N H O
δ+
and therefore can dissolve readily in water.
H
Base Properties
H δ+
Primary aliphatic amines act as Bronsted-Lowry Bases because the
lone pair of electrons on the nitrogen is readily available for forming a CH3NH2 +H2O  CH3NH3+ +OH-
dative covalent bond with a H+ and so accepting a proton.
Primary aliphatic amines are stronger bases than ammonia as the

alkyl groups are electron releasing and push electrons towards the NH3 (aq) +H2O (l)  NH4+(aq) +OH-(aq)
nitrogen atom and so make it a stronger base.
Secondary amines are stronger bases than primary amines because they have more alkyl groups that are
substituted onto the N atom in place of H atoms. Therefore more electron density is pushed onto the N atom (as
the inductive effect of alkyl groups is greater than that of H atoms).
One might expect using the same trend that tertiary amine would be the strongest amine base but the trend does
not hold. The tertiary amines and corresponding ammonium salts are less soluble in water and this makes them
less strong bases than the secondary amines. (This point will not be examined)
Base strength of aromatic amines NH2

Primary aromatic amines such as Phenylamine do not form basic solutions because the
lone pair of electrons on the nitrogen delocalise with the ring of electrons in the benzene
ring. This means the N is less able to accept protons. phenylamine
Reactions with acids
Amines as bases react with acids to form ammonium salts.

CH3NH2 (aq) +HCl (aq)  CH3NH3+Cl-(aq) Addition of NaOH to an ammonium salt
Methylamine methylammonium chloride will convert it back to the amine
2CH3NH2 (aq) +H2SO4 (aq)  (CH3NH3+)2 SO42- (aq)
These ionic salts will be solid crystals, if
the water is evaporated, because of the
The ionic salts formed in this reaction means that the strong ionic interactions.
compounds are soluble in the acid.
e.g. Phenylamine is not very soluble in water but
phenylammonium chloride is soluble
Making a basic buffer from an amine

Basic buffers can be made from combining a weak base with a salt of that weak base
e.g. Ammonia and ammonium chloride
Methylamine and methylammonium chloride
Ethylamine and ethylammonium chloride
Formation of complex ions
The lone pair of electrons on the nitrogen enable amines to act as ligands and form dative covalent bonds
into transition metal ions to form coloured complex ions.
4 CH3CH2NH2 + Cu(H2O)62+ [Cu(CH3CH2NH2)4(H2O)2] 2+ +4H2O
This is a similar ligand exchange reaction to the one where ammonia acts as the ligand
4NH3 + Cu(H2O)62+ [Cu(NH3)4(H2O)2] 2+ + 4H2O

light blue solution deep blue solution
Reaction of primary Amines with halogenoalkanes forming secondary amines
Amines will react with halogenoalkanes in a similar way to the reaction of ammonia with
halogenoalkanes via a nucleophilic substitution reaction
2CH3CH2NH2+ CH3CH2Br CH3CH2NH2CH2CH3+ CH3CH2NH3Br
H
+
H3C C Br H3C CH2 NH2 CH2 CH3 Br -
H
:
CH3CH2NH2
+
H3C CH2 NH CH2 CH3 H3C CH2 NH CH2 CH3 + CH3CH2NH3Br
:NH2CH2CH3
Diethylamine
H
The secondary amine formed can also then react with more halogenoalkane to form a tertiary
amine and subsequently on to what is called a quaternary ammonium salt
Where RX is the haloalkane
H R R
H
RX RX RX
+
H N: R N: R N: R N R
R R R R
Reaction with primary amines with acyl chlorides
Change in functional group: acyl chloride  secondary amide

RCOCl +2CH3NH2  RCONHCH3 + CH3NH3+Cl-
O O
CH3 C + 2CH3NH2  CH 3 C NH CH 3 + CH3NH3+Cl-
Cl N-methylethanamide
Paracetamol is made by the reaction of an aromatic amine with

an acyl chloride to produce an amide
O
CH3 C
Cl O
HO NH2 HO NH C CH3
Paracetamol
The preparation of primary aliphatic amines
1. Forming a primary amine in a one step reaction of halogenoalkanes with ammonia
Primary amines can be formed by the nucleophilic substitution reaction between halogenoalkanes and ammonia in
a one step reaction. However, as the lone pair of electrons is still available on the N in the amine formed, the
primary amine can react in the same nucleophilic way in a successive series of reactions forming secondary, tertiary
amines and quaternary ammonium salts.
This is therefore not a good method for making a primary amine because of the further reactions. It would mean the
desired product would have to be separated from the other products.
CH3CH2Br + 2NH3  CH3CH2NH2 + NH4Br Ammonia dissolved in ethanol is the initial nucleophile
H H
+ In the first step of the mechanism the nucleophile
H3C C Br H3C C NH3 Br -
attacks the halogenoalkane to form an intermediate
H
3HN:
H
H H
+ In the second step of the mechanism a second
H3C C NH2 H3C C NH2 + NH4Br ammonia removes a proton from the
:NH3 intermediate (acts as base) to form the amine
H H H
Using an excess of Ammonia can limit the further

subsequent reactions and will maximise the amount of
primary amine formed
2. Preparing Amines from Nitriles

Using the method above of reacting halogenoalkanes and ammonia is not an efficient method for preparing a
high yield of the primary amine because of the further substitution reactions that occur.
A better method is to use the following reactions
Step 1. convert halogenoalkane to nitrile by using KCN in ethanol (heat under reflux)
CH3CH2Br + CN-  CH3CH2CN + Br -

Step 2. reduce nitrile to amine by using LiAlH4 in ether or by reducing with H2 using a Ni catalyst
CH3CH2CN + 4[H] CH3CH2CH2NH2
A disadvantage of this method is that it is a two step reaction that may therefore have a low yield. Also
KCN is toxic.
Reducing nitroarenes to aromatic amines
The nitro group on an arene can be reduced an amine group as follows
Reagent: Sn and HCl or Fe and HCl NO 2 NH2

Conditions: Heating + 6[H] + 2H2O
Mechanism:reduction
phenylamine
nitrobenzene
As the reaction is carried out in HCl the salt C6H5NH3+Cl- will be formed.
Reacting this salt with NaOH will give phenylamine.
The phenylamine formed in this reaction is best

separated from the reaction mixture by steam distillation.
Forming Amides
Aliphatic amines and phenylamine can react with acyl chlorides to form amides in a nucleophilic
addition-elimination reaction- see chapter 17C for more details.

secondary amide
RCOCl +2CH3NH2  RCONHCH3 + CH3NH3+Cl-

O
O + CH3NH3+Cl-
CH3 C + 2CH3NH2  CH3 C NH CH3
Cl
N-methylethanamide
Condensation Polymerisation
In condensation polymerisation there are two different monomers
The two most common types of that add together and a small molecule is usually given off as a
condensation polymers are side-product e.g. H2O or HCl.
polyesters and polyamides which
involve the formation of an ester The monomers usually have the same functional group on both ends
linkage or an amide linkage. of the molecule e.g. di-amine, di carboxylic acid, diol, diacyl chloride.
Forming polyesters and polyamide uses these reactions we met earlier in the course
Carboxylic Acid + Alcohol  Ester + water Carboxylic Acid + Amine  amide + water
Acyl chloride + Alcohol  Ester + HCl Acyl chloride + Amine  amide + HCl
If we have the same functional group on each end of molecule we can make polymers so we have the
analogous equations:
dicarboxylic acid + diol  poly(ester) + water dicarboxylic acid + diamine  poly(amide) + water
diacyl dichloride + diol  poly(ester) + HCl diacyl dichloride + diamine  poly(amide) + HCl
Using the carboxylic acid to make the ester or amide would need an acid catalyst and would only give an
equilibrium mixture. The more reactive acyl chloride goes to completion and does not need a catalyst but does
produce hazardous HCl fumes.
Terylene- a common polyester

O O
O O
n + n HO CH CH OH C C O CH2 CH2 O + 2n-1 H2O
C C 2 2
n
HO OH Ethane-1,2-diol
The -1 here is because at
Benzene-1,4-dicarboxylic acid
each end of the chain the H
Terylene fabric is used in clothing, tire cords and OH are still present
O O O O
n C (CH2)3 C + n HO OH + 2n-1 HCl
C (CH2)3 C O O
Cl Cl n
Pentanedioyl dichloride Benzene-1,4-diol
Nylon 6,6 - a common polyamide

O O
O O H H
N (CH2)6 N
n C (CH2)4 C +n C (CH2)4 C N (CH2)6 N + 2n-1 H2O
H H
HO OH
hexanedioic acid Hexane-1,6-diamine H H
n
The 6,6 stands for 6 carbons in each of the monomers. Different length carbon chains produce different
polyamides
Kevlar- a common polyamide
O O
n HO2C CO2H + n H2N NH2 + 2n-1 H2O
N N C C
H H n
Note on classification for condensation polymers
If asked for type of polymer: It is polyamide or polyester
Whereas type of polymerisation is condensation
It is also possible for polyamides and polyesters to form from one monomer, if that monomer
contains both the functional groups needed to react
O O O O
HO (CH2)3 C O (CH2)3 C O (CH2)3 C O (CH2)3 C
Cl
3 repeating units
O O O O
H2N C
N C N C N C
OH
H H H
3 repeating units
Chemical reactivity of condensation polymers The reactivity can be explained by the presence of
polyesters and polyamides can be broken down by polar bonds which can attract attacking species
hydrolysis and are, therefore, biodegradable such as nucleophiles and acids
Hydrolysis
Polyesters and polyamides can be hydrolysed by acid and alkali
The hydrolysis will result in the original monomers forming- although the carboxylic acid or amine group
will be in salt form depending on whether the conditions are alkaline or acidic
O O
O
+
HCl OH H 3N +
C (CH2)4 C N (CH2)6 N
HO
+ NH 3
H H O
n
NaOH O
-
-CO(CH2)4CONHC(CH3)2CH2O- - O
O + H2N
This polymer has both an amide and O
OH
ester link
Intermolecular bonding between condensation polymers chains

Polyesters have permanent dipole forces between the Cδ+=Oδ- groups in the different chains in
addition to the London forces between the chains.
Polyamides (and proteins) have hydrogen δ-

:
O Oδ- O
bonding between the lone pairs on oxygen in δ-
N C N C Nδ- C
Cδ+=Oδ- groups and the H in the Nδ- —Hδ+ δ+ δ+
H H δ+ H δ+
groups in the different chains.
There are also Permanent dipole-permanent
dipole forces because the polar C=O
:
O δ- Oδ- O
bond and polar C-N bond δ- δ-
N C N C N C
There are also London forces which are large δ+ δ+
because there are many electrons in the H H Hδ+
δ+
molecule
Polyamides will therefore have higher melting
points than polyesters.
Amino Acids
The simplest amino acid is

General structure of an amino acid NH2 CH2 CO2H
glycine, where the R is an H
NH2 CH CO2H
R
The R group can be a variety of
different things depending on what
amino acid it is.
Naming amino acids

CO2H Some amino acids have an extra CO2H
You do not need to know any carboxylic acid or an amine
CH2 CH2
common names for the 20 group on the R group. These are
essential amino acids. We NH2 C CO2H classed as acidic or basic NH2 C CO2H
should, however, be able to H 2-aminobutanedioic acid (respectively) amino acids H
name given amino acids using Aspartic acid
IUPAC organic naming OH
CO2H
CH2
H C (CH2)4 NH2
NH2 CH2 CO2H NH2 C CO2H Lycine (basic)
H 2-amino-3-
H2N 2,6-diaminohexanoic acid
(2-)aminoethanoic acid
hydroxypropanoic acid
Zwitterions
R R
The no charge form of an amino acid never occurs. + -
The amino acid exists as a dipolar zwitterion. H2N C CO2H H3N C CO2
H H
Amino acids are often solids Zwitterion
The ionic interaction between zwitterions explains the relatively high melting points of amino acids as
opposed to the weaker hydrogen bonding that would occur in the no charge form.
Acidity and Basicity

The amine group is basic and the carboxylic acid group is acidic. Amino acids act as weak buffers and will
only gradually change pH if small
R OH- R H+ R amounts of acid or alkali are added to the
- + - +
H2N C CO2 H3N C CO2 H3N C CO2H amino acids.
+NH -CH -CO - + HCl  Cl- NH3+-CH2-CO2H
H H H 3 2 2
H+ OH-
+NH -CH -CO - + NaOH  NH2-CH2-CO2-Na+ +H2O
Species in Species in Species in 3 2 2
alkaline solution neutral solution acidic solution
High pH Low pH
-
The extra carboxylic acid or amine groups COO
on the R group will also react and change CH2 Aspartic acid in high pH
form in alkaline and acid conditions -
NH 2 C COO
H
Chromatography of Amino Acids
A mixture of amino acids can be separated by Method
chromatography and identified from the amount Take chromatography paper
they have moved. and draw a pencil line 1.5cm
from bottom.
With a capillary tube put a small
Rf value = distance moved by amino acid
drop of amino acid on pencil line
distance moved by the solvent Roll up paper and stand it in a
large beaker.
Each amino acid has its own Rf value. The solvent in the beaker
Compare an unknown amino acid’s Rf should be below the pencil line.
value with known values in a data book to Allow to stand for 20 mins and
identify the amino acid mark final solvent level
Spray paper with ninhydrin and
put in oven
If ninhydrin is sprayed on an amino acid and then heated for 10 minutes then red to blue spots appear.
This is done because amino acids are transparent and cannot be seen.
Optical Activity Optical isomers have similar

All amino acids, except H H
physical and chemical
glycine, are chiral because properties, but they rotate
there are four different groups C C
H2N CO2H HO2C plane polarised light in
around the C NH2 different directions.
CH3 CH3
They rotate plane polarised light.
Proteins CH3
Proteins are polymers made from H3C CH3 S

combinations of amino acids. CH HS CH2
The amino acids are linked by peptide links,
CH3 O CH2 O CH2 O CH2 O
which are the amide functional group.
H N CH C N CH C N CH C N CH C O H
O O O H H H H
NH CH C NH CH C NH CH C
R R R
Dipeptides
Dipeptides are simple combination molecules of For any two different amino acids there are two possible
two amino acids with one amide (peptide) link. combinations of the amino acids in the dipeptide.
HO HO
HO
CH3 H
Can make CH3 H CH2 CH2 CH3
CH2 or
H2N C CO2H +
H2N C C N C CO2H H2N C C N C CO2H
H H2N C CO2H
H H H O H
O
H
O δ- O
Importance of hydrogen bonding in proteins
:
δ-
N CH C N CH C
The 3D arrangement of amino acids with the δ+
polypeptide chain in a corkscrew shape is held in δ+
H R H R
place by Hydrogen bonds between the H of –Nδ-
:
—Hδ+ group and the –O of Cδ+=Oδ- δ-
O O
δ-
N CH δ+ C N CH C
H R H R
Hydrolysis of di-peptides/proteins
If proteins are heated with dilute acid or alkali they can be The composition of the protein
hydrolysed and split back in to their constituent amino acids. molecule may then be deduced by
using paper chromatography
H3C CH3
CH H3C CH3
CH
CH3 O CH2 O CH3 O
H+
H N CH C N CH C O H + CH2 O
H3N CH C O H + +
H3N CH C O H
H H
O H 3C CH 3
CH
C OH O H 3C CH 3
CH2 O H 2C O - CH
C O
NaOH
H N CH C N CH C O H CH2 O H 2C O
+
- -
H 2N CH C O H 2N CH C O
H H
Other reactions of amino acids

The carboxylic acid group and amine group in amino acids can undergo the usual reactions of these functional groups met
in earlier topics. Sometimes questions refer to these.
e.g. Esterification reaction
CH3
CH3 O
H+ +
H2N C CO2H + CH3OH H3N C C O CH3 + H2O
H H
CO 2 H O
If the R group contains
CO2H H C (CH 2) 4 NH C CH 3 a amine or carboxylic
H C (CH2)4 NH2 + 2CH3COCl NH acid then these will do
H2N the same reactions as
C O the α amine and
CH3 carboxylic groups
18C. Synthetic Routes
KOH aqueous
dihalogenoalkane heat under reflux
Nucleophilic substitution
poly(alkene) diol
Br2, Cl2 KMnO4
room temp oxidation
Electrophilic addition
high pressure
alkane
Catalyst Br2, Cl2
H2, Nickel Catalyst
polymerization UV light
addition/reduction
alkene HBr, HCl
Free radical Substitution
room temp
Electrophilic addition
KOH alcoholic heat
halogenoalkane
conc. H3PO4 under reflux
H2O (g) Elimination
Catalyst: Elimination,
dehydration
Conc H3PO4 CN– and
PCl5, NaBr/H2SO4 P + I2
,
ethanol
Heat under reflux Nucleophilic
substitution KOH aqueous Alcoholic NH3 substitution
heat under reflux heat under pressure
Nucleophilic substitution Nucleophilic
LiAlH4
alcohol substitution
Reduction Caboxylic acid + H2SO4

heat amine LiAlH4
nitrile
LiAlH4 K2Cr2O7/H+ esterification
Reduction
Reduction
LiAlH4
If primary If secondary Reduction haloalkane
heat gently and distill heat under reflux NuSub
partial oxidation oxidation
Acyl chloride
2o amine room temp
3o amine Nu add/elim
aldehyde ketone
HCN + KCN secondary
Nucleophilic addition amide
K2Cr2O7/H+
heat under reflux + Esters and amides
excess oxidising agent can be hydrolysed
Oxidation hydroxynitrile by NaOH and acids
1o amine
Alcohol + H2SO4 room temp Primary
heat ester amide
carboxylic acid esterification
Alcohol
PCl5 room temp NH3 room temp
H2O room
temp Acyl chloride
Acid hydrolysis
Heat with HCl
Aromatic synthetic routes
Br
CH2CH3
chloroalkane and
anhydrous AlC3
Hydrogen Electrophilic catalyst
Nickel substitution
catalyst Br2
FeBr3
conc nitric acid +

conc sulphuric acid
Electrophilic NO2
substitution
Sn and HCl NH2
NH CH3
reduction CH3Cl
Nu sub
acyl chloride in the presence
of anhydrous aluminium
chloride catalyst
Electrophilic substitution
O CH3COCl
C
CH3 O
NaCN + H2SO4 NH C CH3
Nu Add
LiAlH4 H
Red Nu Add
O
H
C CN
O
CH CH 3
CH3
HCl/heat
H
O O
CH3CO2H + H2SO4
heat C C
esterification OH
CH3
O
H3C CH O C CH3
Grignard Reactions
Grignard Reagent is used to increase the length of the carbon chain in a molecule
Preparing Grignard Reagent

A halogenoalkane is dissolved in dry ether and reacted with magnesium to
produce the reactive Grignard Reagent
This Grignard reagent is highly reactive and the

CH3CH2I + Mg  CH3CH2MgI
alkyl group can be considered to have a
Ethyl magnesium iodide negative charge. The R- [+MgI] and so contains
Grignard Reagent
a nucleophilic carbon atom
Reactions of Grignard Reagent
Reactions with carbonyls

With methanal will produce a primary alcohol
H2O
CH3CH2MgI + HCHO  CH3CH2CH2OH + Mg(OH)I
RMgI + HCHO  RCH2OH + Mg(OH)I
With other aldehydes will produce secondary alcohols

CH3
H2O
CH3CH2MgI + CH3CHO  H3C CH2 C OH + Mg(OH)I
H
H2O
RMgI + R’CHO  RCH(OH)R’ + Mg(OH)I
With ketones will produce tertiary alcohols

CH3
H3C CH3 H2O
CH3CH2MgI + C  H3C CH2 C OH + Mg(OH)I
O CH3
H2O
RMgI + R’COR”  RR’C(OH)R” + Mg(OH)I
Reaction with carbon dioxide

With CO2 will produce a carboxylic acid
H2O
CH3CH2MgI + CO2  CH3CH2CO2H + Mg(OH)I
The carbon chain can also be increased by the introduction of a nitrile group into a compound by either
reacting a halogenoalkane with KCN (see chapter 6D) or producing hydroxynitriles from carbonyls (see
chapter 17B)
Organic techniques
It’s important to be able to
draw and label this
Distillation apparatus accurately.
thermometer Don’t draw lines between
In general used as separation technique to separate an flask, adaptor and
organic product from its reacting mixture. Need to condenser.
collect the distillate of the approximate boiling point
range of the desired liquid.
Classic AS reaction using distillation Liebig condenser

Reaction: primary alcohol  aldehyde
Reagent: potassium dichromate (VI) solution and
Conditions: use a limited amount of dichromate
and warm gently and distil out the aldehyde as it
forms [This prevents further oxidation to the Water
carboxylic acid] out
CH3CH2CH2OH + [O]  CH3CH2CHO + H2O
Round Water in
Observation
bottomed
Orange dichromate solution changes to green
flask
colour of Cr3+ ions
Heat
Reflux
Reflux is used when heating organic reaction mixtures for long Water out
periods. The condenser prevents organic vapours from escaping
by condensing them back to liquids.
condenser
Never seal the end of the condenser as the build up of gas
pressure could cause the apparatus to explode. This is true of any
apparatus where volatile liquids are heated
Classic AS reaction using reflux

Reaction: primary alcohol  carboxylic acid Water in
Reagent: potassium dichromate(VI) solution and dilute
sulphuric acid
Conditions: use an excess of dichromate, and heat
under reflux: (distill off product after the reaction Round
has finished using distillation set up) bottomed
CH3CH2CH2OH + 2[O]  CH3CH2CO2H + H2O flask
Observation
Orange dichromate solution changes to green colour of
Cr3+ ions
Heat
Anti-bumping granules are added to the flask in both distillation and reflux to prevent vigorous,
uneven boiling by making small bubbles form instead of large bubbles
It’s important to be able to draw and label this apparatus accurately.

• Don’t draw lines between flask and condenser.
• Don’t have top of condenser sealed
• Condenser must have outer tube for water that is sealed at top and bottom
• Condenser must have two openings for water in and out that are open
Purifying an organic liquid General method
• Put the distillate of impure product into a separating

funnel
• wash product by adding either Sodium hydrogencarbonate will
• sodium hydrogencarbonate solution , shaking neutralise any remaining reactant acid.
and releasing the pressure from CO2 produced. Sodium chloride will help separate the
• Saturated sodium chloride solution organic layer from the aqueous layer
•Allow the layers to separate in the funnel, and then run and The layer with lower density will Separating
discard the aqueous layer. be the upper layer. This is usually funnel
the organic layer
•Run the organic layer into a clean, dry conical flask and add
three spatula loads of drying agent (e.g. anhydrous sodium
The drying agent should
sulphate, calcium chloride) to dry the organic liquid. When
•be insoluble in the organic liquid
dry the organic liquid should appear clear.
• not react with the organic liquid
• Carefully decant the liquid into the distillation flask
Decant means carefully pour off organic liquid
•Distill to collect pure product leaving the drying agent in the conical flask
Purifying an organic solid: Recrystallisation Used for purifying aspirin
Step Reason
1. Dissolve the impure compound in a minimum An appropriate solvent is one which will dissolve both
volume of hot (near boiling) solvent. compound and impurities when hot and one in which
the compound itself does not dissolve well when cold.
The minimum volume is used to obtain saturated
solution and to enable crystallisation on cooling (If
excess (solvent) is used, crystals might not form on
cooling)
2. Hot filter solution through (fluted) filter paper This step will remove any insoluble impurities and
quickly. heat will prevent crystals reforming during filtration
3. Cool the filtered solution by inserting beaker in ice Crystals will reform but soluble impurities will remain
in solution form because they are present in small
quantities so the solution is not saturated with the
impurities. Ice will increase the yield of crystals
4. Suction filtrate with a buchner flask to separate The water pump connected to the Buchner flask
out crystals reduces the pressure and speeds up the filtration.
5 Wash the crystals with distilled water To remove soluble impurities
6. Dry the crystals between absorbent paper
Loss of yield in this process

• Crystals lost when filtering or washing
• Some product stays in solution after recrystallisation
• other side reactions occurring Buchner flask
If the crystals are not dried properly the mass will be larger
than expected which can lead to a percentage yield >100%
Steam distillation steam
in
In steam distillation steam is passed into

the mixture and the product vapour is
distilled off with the water and condensed
Advantage of steam distillation:

The product distils at a lower temperature
which can prevents decomposition of the
product if it has a high boiling point
Water
out
Water
in
Solvent extraction
Mix organic solvent and oil-water mixture in a

separating funnel then separate the oil layer.
Distil to separate oil from organic solvent
Add anhydrous CaCl2 to clove oil to dry oil
Decant to remove CaCl2
Separating funnel
Safety and hazards
A hazard is a substance or procedure that can has the RISK: This is the probability or chance that
potential to do harm. harm will result from the use of a
Typical hazards are toxic/flammable /harmful/ hazardous substance or a procedure
irritant /corrosive /oxidizing/ carcinogenic
Irritant - dilute acid and alkalis- wear googles Hazardous substances in low
Corrosive- stronger acids and alkalis wear goggles concentrations or amounts
Flammable – keep away from naked flames will not pose the same risks
Toxic – wear gloves- avoid skin contact- wash hands after use as the pure substance.
Oxidising- Keep away from flammable / easily oxidised materials
Measuring melting point
One way of testing for the degree of purity is to determine the melting
“point”, or melting range, of the sample.
Thermometer with
If the sample is very pure then the melting point will be a capillary tube
sharp one, at the same value as quoted in data books. strapped to it
containing sample
If impurities are present (and this can include solvent from the
recrystallisation process) the melting point will be lowered and Heating oil- needs
the sample will melt over a range of several degrees Celsius to have boiling point
higher than samples
melting point and
Melting point can be measured in an electronic melting point low flammability
machine or by using a practical set up where the capillary tube is
strapped to a thermometer immersed in some heating oil.
In both cases a small amount of the salt is put into a capillary tube.
Heat
Comparing an experimentally determined melting point
value with one quoted in a data source will verify the
degree of purity.
Sometimes an error may occur if the temperature on the thermometer is not the same as the temperature in
the actual sample tube.
Measuring boiling point

Purity of liquid can be determined by measuring a boiling point. This can be
done in a distillation set up or by simply boiling a tube of the sample in an To get a correct measure
heating oil bath. of boiling point the
thermometer should be
Pressure should be noted as changing pressure can change the boiling above the level of the
point of a liquid surface of the boiling liquid
and be measuring the
temperature of the
Measuring boiling point is not the most accurate method of identifying a saturated vapour.
substance as several substances may have the same boiling point.
Combustion Analysis
0.328 g of a compound containing C,H and O was burnt completely in excess oxygen,
producing 0.880 g of carbon dioxide and 0.216 g of water. Use these data to calculate
the empirical formula of the compound.
Work out moles of CO2 = Mass of CO2/Mr of CO2

= 0.88/44
=0.02mol
Moles of C in compound = moles of CO2 Mass of C in = mol of C x 12
= 0.02 mol compound =0.02 x12
=0.24g
Work out moles of H2O = Mass of H2O /Mr of H2O
= 0.216/18
=0.012mol
Moles of H in compound = 2 x moles of H2O Mass of H in = mol of H x 1

= 0.024 mol compound =0.024 x1
=0.024g
Work out mass of O = mass of compound – mass of C – mass of H

in compound = 0.328 – 0.24 -0.024
=0.064
Work out moles of O = Mass of O /Ar of O

in compound = 0.064/16
= mol 0.004
Work out molar ratio

of 3 elements (divide C = 0.02/0.004 H = 0.024/0.004 O = 0.004/0.004
by smallest moles) =5 =6 =1
empirical formula = C5H6O
See notes in chapter 19 on spectroscopy for mass spec, IR, and NMR
Bringing it all together
C H O
1. Work out empirical formula
66.63/12 11.18/1 22.19/16
Elemental analysis C 66.63% H 11.18% O 22.19%
=5.5525 =11.18 =1.386875
=4 =8 =1
2. Using molecular ion peak m/z value from mass

spectrum calculate Molecular formula Mr empirical formula C4H8O = 72
molecular ion peak m/z value= 144 If Mr molecular formula 144 then
compound is C8H16O2
3. Use IR spectra or functional group C8H16O2 could be an ester, carboxylic acid or combination of
chemical tests to identify main alcohol and carbonyl. Look for IR spectra for C=O and O-H
bonds/functional group bonds
There is a C=O but no

O-H absorptions, so
must be an ester.
C-H
C=O
CH3
4. Use NMR spectra to give details of carbon chain singlet of area 9 H3C C H
At δ =0.9 CH3
4 peaks – only 4 different environments. Means 3 CH3 groups
9
Peak at δ 4 shows H–C–O Peak at δ 1.2

Peak at δ 2.2 shows H–C=O
shows R-CH3
Area 2 suggests CH2 Area 2 suggests CH2 Area 3 means CH3
Quartet means next to a Singlet means adjacent to Triplet means next
CH3 C with no hydrogens to a CH2
H H3C CH3
H O
H3C O C H
H3C O C C H 2
2 3
H
H
5 4 δ ppm 3 2 1
Put all together to give final structure
CH3 O
H3C C CH2 C O CH2 CH3
CH3
Testing for Organic Functional Groups
Functional group Reagent Result
Alkene Bromine water Orange colour

decolourises
Alcohols + carboxylic acids PCl5 Misty fumes of HCl
produced
Alcohols, phenols, Sodium metal Efferevesence due to H2
carboxylic acids gas
Carbonyls 2,4,DNP Orange/red crystals
produced
Aldehyde Fehlings solution Blue solution to red
precipitate
Aldehyde Tollens Reagent Silver mirror formed
Carboxylic acid Sodium carbonate Effervescence of CO2

evolved
1o 2o alcohol and Sodium dichromate and Orange to green colour
aldehyde sulphuric acid change
chloroalkane Warm with silver nitrate Slow formation of white
precipitate of AgCl
Acyl chloride Silver nitrate Vigorous reaction- steamy
fumes of HCl- rapid white
precipitate of AgCl
Tollen’s Reagent Fehling’s solution

Reagent: Tollen’s Reagent formed by mixing aqueous Reagent: Fehling’s Solution containing blue Cu 2+ ions.
ammonia and silver nitrate. The active substance Conditions: heat gently
is the complex ion of [Ag(NH3)2]+ . Reaction: aldehydes only are oxidised by Fehling’s
Conditions: heat gently Solution into a carboxylic acid and the copper ions
are reduced to copper(I) oxide .
Reaction: aldehydes only are oxidised by Tollen’s
reagent into a carboxylic acid and the silver(I) Observation: Aldehydes :Blue Cu 2+ ions in solution
change to a red precipitate of Cu 2O. Ketones do
ions are reduced to silver atoms not react
Observation: with aldehydes, a silver mirror forms
coating the inside of the test tube. Ketones result CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+
in no change.
CH3CHO + 2Ag+ + H2O  CH3COOH + 2Ag + 2H+
The presence of a carboxylic acid can be tested by

addition of sodium carbonate. It will fizz and produce
carbon dioxide
2CH3CO2H + Na2CO3  2CH3CO2-Na+ + H2O + CO2
19. Spectroscopy and chromatography
The effect of different types of radiation on molecules
i infrared in analysis – infra red energy causes bonds to vibrate. This can be used to identify the types
of bond in a molecule
ii microwaves for heating- certain molecules absorb the microwaves causing them to rotate
iii radio waves in nmr – can cause the hydrogen nucleus to change its spin state. This can give us
information about the arrangements of hydrogens in a molecule.
iv ultraviolet in initiation of reactions – UV energy can break bonds such as the Cl-Cl bond or C-Cl
bond
NMR spectroscopy
NMR spectroscopy involves interaction of materials with the low- The radio waves used in
energy radiowave region of the electromagnetic spectrum proton nmr cause the
hydrogen nucleus to change
NMR spectroscopy is the same technology as that used in ‘magnetic its spin state.
resonance imaging’ (MRI) to obtain diagnostic information about
internal structures in body scanners e.g. scanning for brain disorders
Equivalent Hydrogen atoms.

In addition the intensity (integration value)
In an H NMR spectrum, there is one
of each signal is proportional to the number
signal for each set of equivalent H atoms.
of equivalent H atoms it represents.
Ha H b 3 Ha Hb Hc H d
a
a H Hd
H C C O C C C C
c aH Hc H
H Hb H H C Ha d
a 2 a
Ha
4sets of equivalent H’s:
Ethanol has 3 ratio 6:1:2:3
1
groups of different
O
hydrogen atoms
H3C C CH3 1 signal
a a
a b O c
CH3c H3C CH2 C O CH3
O
a b c
H3C CH2 C O C CH3
3 sets of equivalent H’s: ratio 3:2:3
c
CH3
Br
3 sets of equivalent H’s: ratio 3:2:9
a b c
H3C CH CH2 CH3 CH CH2 CH3
a b c d
3 sets of equivalent 4 sets of equivalent H’s: ratio 3:1:2:3
H’s: ratio 3:1:2
Solvents
This means that in the H NMR the
Samples are dissolved in solvents without any 1H atoms, e.g. CCl4, CDCl3.
solvent will not give any peaks
Calibration and shift
A small amount of TMS (tetramethylsilane) is added

to the sample to calibrate the spectrum
CH3 The spectra are recorded on a
TMS is used because:
scale known as the chemical
•its signal is away from all the others
H3C Si CH3 shift (δ), which is how much the
•it only gives one signal
field has shifted away from the
•it is non-toxic
CH3 field for TMS..
•it is inert
•it has a low boiling point and so can be removed tetramethylsilane
from sample easily
The δ is a measure in parts per million (ppm) is a relative 10 9 8 7 6 5 4 3 2 1 0

scale of how far the frequency of the proton signal has δ chemical shift (ppm)
shifted away from that for TMS.
H NMR shift
The δ depends on what other atoms/groups are near the
H – more electronegative groups gives a greater shift.
3
O
H3C CH2 C O CH3
δ ppm
H H O
H C C C
H H O H
2
δ ppm
Spin-Spin coupling in H NMR
Nuclei in identical chemical
In high resolution H NMR each signal in the spectrum can be split into environments do not show
further lines due to inequivalent H’s on neighbouring C atoms. coupling amongst themselves!
Splitting of peak = number of inequivalent H’s on neighbouring C atoms + 1

a b O c
H3C CH2 C O CH3
signal singlet doublet triplet quartet quintet
The peak due to group a will
be a triplet as it is next to b
appearance (a carbon with 2 H’s)
The peak due to group b will
be a quartet as it is next to a
Split number (a carbon with 3H’s)
1 2 3 4 5
of peaks
The peak due to group c will
number of be a singlet as it is next to a
neighbouring carbon with no H’s)
0 1 2 3 4
inequivalent
H atoms
For 6 split peaks use the
relative size 1:1 1:2:1 1:3:3:1 1:4:6:4:1 term hextet or multiplet
H O H H The peak due to group c will

a
be a triplet as it is next to a
H C C O C C H carbon with 2 H’s
a H Shift 0.7-1.2
b H H c
Integration trace 3
c
The peak due to group a will The peak due to group b will
b
be a singlet as it is next to be a quartet as it is next to
a carbon with 0 H’s a carbon with 3 H’s
Shift 2.1-2.6 Shift 3.7 -4.1
Integration trace 3 Integration trace 2
ppm
Mass spectrometry
Measuring the Mr of an organic molecule Spectra for C4H10
If a molecule is put through a mass spectrometer Mass spectrum for butane

it will often break up and give a series of peaks
caused by the fragments. The peak with the 43
Molecular ion
largest m/z, however, will be due to the complete
C4H10+
molecule and will be equal to the Mr of the
molecule. This peak is called the parent ion or 29
molecular ion
58
Fragmentation
Molecular ion formed: M → [M]+. + e–
When organic molecules are passed through a mass
spectrometer, it detects both the whole molecule and The molecule loses an electron and
fragments of the molecule. becomes both an ion and a free radical
Several peaks in the mass spectrum occur due to fragmentation. This process produces an ion
The Molecular ion fragments due to covalent bonds breaking: [M]+. → X+ + Y. and a free radical. The ion is
responsible for the peak
Relatively stable ions such as carbocations R+ such as CH3CH2+ and
acylium ions [R-C=O]+ are common. The more stable the ion, the greater
the peak intensity.
The peak with the highest mass/charge ratio will be normally due to the
original molecule that hasn’t fragmented (called the molecular ion) . As
the charge of the ion is +1 the mass/ charge ratio is equal to Mr.

Mass spectrum for butane
C4H10 → [C4H10]+. + e– m/z 58
43
Equations for formation of fragment ions from molecular ions
[C4H10]+. → [CH3CH2CH2]+ + .CH3 m/z 43

29 C4H10 = 58
[C4H10]+. → [CH3CH2]+ + .CH2CH3 m/z 29

Mass spectrum for butanone
CH3CH2COCH3 → [CH3CH2COCH3]+. + e– m/z 72
The high peak 43
at 43 due to [CH3CO]+ Equations for formation of fragment ions from molecular ions
stability of acyl
group [CH3CH2COCH3]+. → [CH3CH2CO]+ + .CH3 m/z 57
29 [CH3CH2CO]+ [CH3CH2COCH3]+. → [CH3CO]+ + .CH2CH3 m/z 43

+.
[CH3CH2]+ 57 [CH3CH2COCH3] [CH3CH2COCH3]+. → [CH3CH2]+ + .COCH3 m/z 29
72
Infrared spectroscopy
Complicated spectra can be obtained than

Certain bonds in a molecule absorb infra-red radiation at provide information about the types of bonds
characteristic frequencies causing the covalent bonds to present in a molecule
vibrate
ABOVE 1500 cm-1 – “Functional group identification”

BELOW 1500 cm-1 – “Fingerprinting”
Complicated and contains many

signals – picking out functional group
signals difficult.
This part of the spectrum is unique for

every compound, and so can be used
as a "fingerprint".
A computer will compare the IR

e.g. C=O 1640 – 1750 cm-1
spectra against a database of known
O-H (acid) 2500- 3300 cm-1 pure compounds to identify the
compound
Use an IR absorption table provided in exam
to deduce presence or absence of particular
bonds or functional groups use spectra to identify particular functional groups limited to data
presented in wavenumber form e.g. an alcohol from an absorption peak
Bond Wavenumber of the O–H bond,
C-O 1000-1300
C=O 1640-1750 Spectra for

butanal
C-H 2850 -3100
O
O-H 2500-3300
H3C CH2 CH2 C
Carboxylic acids Very broad
H
N-H 3200-3500
2000 1500
O-H 3200- 3550
Acohols, phenols broad C=O
Absorption or trough in between 1640-1750 cm-1 range indicates
presence of C=O bond
Always quote the wave number range from the data sheet
Spectra for
O-H absorptions tend ethanoic acid
to be broad
O
Absorption or trough in
between 2500-3300 cm-1 range H3C C
indicates presence of O-H OH
bond in an acid
C=O
Modern breathalysers measure ethanol in the breath by analysis using infrared spectroscopy
Chromatography
The mobile phase may be a liquid or a gas.
The stationary phase may be a solid (as in thin-
Chromatography is an analytical technique that separates
layer chromatography, TLC) or either a liquid or
components in a mixture between a mobile phase and a
solid on a solid support (as in gas
stationary phase.
chromatography, GC)
Separation by column chromatography depends on

the balance between solubility in the moving phase If the stationary phase was polar and the moving
and retention in the stationary phase. phase was non- polar e.g. Hexane. Then non-
polar compounds would pass through the column
more quickly than polar compounds as they would
A solid stationary phase separates by adsorption, have a greater solubility in the non-polar moving
A liquid stationary phase separates by relative solubility phase.
(Think about intermolecular forces)
HPLC stands for high performance liquid

In gas-liquid chromatography GC the mobile phase is
chromatography.
a inert gas such as nitrogen, helium, argon.
HPLC: stationary phase is a solid silica
The Stationary phase is a liquid on an inert solid.
HPLC: mobile phase a liquid
Gas-Liquid Chromatography
Gas-liquid chromatography can be used to separate In gas-liquid chromatography, the mobile

mixtures of volatile liquids. phase is a gas such as helium and the
stationary phase is a high boiling point
The time taken for a particular compound to liquid absorbed onto a solid.
travel from the injection of the sample to where
it leaves the column to the detector is known as Sample in
its retention time. This can be used to identify Flow
a substance. control oven
Some compounds have similar retention times so

will not be distinguished. display
Waste
column outlet
Basic gas-liquid chromatography will tell us how
many components there are in the mixture by the Carrier gas detector
number of peaks. It will also tell us the
abundance of each substance. The area under
each peak will be proportional to the abundance
of that component.
It is also possible for gas-liquid chromatography

machine to be connected to a mass Most commonly a mass spectrometer is combined
spectrometer, IR or NMR machine, enabling all with GC to generate a mass spectra which can be
the components in a mixture to be identified. analysed or compared with a spectral database by
computer for positive identification of each
component in the mixture.
GC-MS is used in analysis, in forensics, environmental
analysis, airport security and space probes.
TLC Chromatography (thin-layer
chromatography)
Method
A mixture can be separated by Take chromatography paper and
chromatography and identified from the draw a pencil line 1.5cm from
amount they have moved. (Can be used with bottom.
With a capillary tube put a small
mixtures of amino acids)
drop of amino acid on pencil line
Roll up paper and stand it in a large
Rf value = distance moved by amino acid beaker.
The solvent in the beaker should be
distance moved by the solvent
below the pencil line.
Allow to stand for 20 mins and mark
Each substance has its own Rf value final solvent level
Spray paper with ninhydrin and put
Measure how far each spot travels relative in oven
to the solvent front and calculate the Rf
value.
Some substances won't separate because similar
Compare Rf values to those for known
compounds have similar Rf values. So some spots may
substances.
contain more than one compound
Bringing it all together
C H O
1. Work out empirical formula
66.63/12 11.18/1 22.19/16
Elemental analysis C 66.63% H 11.18% O 22.19%
=5.5525 =11.18 =1.386875
=4 =8 =1
2. Using molecular ion peak m/z value from mass

spectrum calculate Molecular formula Mr empirical formula C4H8O = 72
molecular ion peak m/z value= 144 If Mr molecular formula 144 then
compound is C8H16O2
3. Use IR spectra to identify main C8H16O2 could be an ester, carboxylic acid or combination of
bonds/functional group alcohol and carbonyl. Look for IR spectra for C=O and O-H
bonds
There is a C=O but no

O-H absorptions, so
must be an ester.
C-H
C=O
CH3
H3C C
4. Use NMR spectra to give details of carbon chain singlet of area 9
At δ =0.9 CH3
4 peaks – only 4 different environments. Means 3 CH3 groups
9
Peak at δ 4 shows H–C–O Peak at δ 1.2

Peak at δ 2.2 shows H–C=O
shows R-CH3
Area 2 suggests CH2 Area 2 suggests CH2 Area 3 means CH3
Quartet means next to a Singlet means adjacent to Triplet means next
CH3 C with no hydrogens to a CH2
H CH3
H O
O C H
O C C H 2
2 3
H
H
5 4 δ ppm 3 2 1
Put all together to give final structure

CH3 O
H3C C CH2 C O CH2 CH3
CH3

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1.

Atomic Structure and Periodic Table

Particle Position Relative Mass Relative Charge

Mass Number 7 Li Atomic Symbol

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

DEFINITION: Relative atomic mass is the average mass of one atom

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

THE MASS SPECTROMETER

Calculating relative atomic mass

Fig: spectra for

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

For above example of Mg

Mass spectra for Cl2 and Br2

These lead to the following spectra caused by the diatomic molecules

Measuring the Mr of a molecule Spectra for C4H10

Uses of Mass spectrometers

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

Successive ionisation energies

Why are successive ionisation energies always larger?

period is called periodicity.

1500 The pattern in the first ionisation energy

Q. Why has Helium the largest first ionisation energy?

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

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

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

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

The A-level model

Writing electronic structure using letters and numbers •s sublevels are

Number of main Name of

The arrows going in the

When filling up sub levels with several

Electronic structure for ions

Classification of elements in s, p, d blocks

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

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

Atomic radius 0.18

atomic radius (nm)

1st ionisation energy

Melting and boiling points

makes the bonding stronger. High energy is needed to break

Mg goes from 1s2 2s2 2p63s2

O goes from 1s2 2s2 2p4 to

Ionic crystals have the structure of giant lattices of ions

An Ionic bond is the strong electrostatic force of attraction

There are increasing numbers of protons from N to F

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

X-ray diffraction: Electron density map of NaCl

Physical properties of Ionic Compounds

A covalent bond strong and is caused by the electrostatic attraction

The X-ray diffractions for the hydrogen

In a covalent compound there is significant electron

Electron Configuration Diagrams

Effect of multiple bonds on bond strength and length.

The ammonium ion NH4+

The direction of the arrow

Name No No lone Diagram Bond angle Examples

Trigonal 3 1 .. 107 NCl3 ,PF3 ,ClO3

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

Trigonal 5 0 F 120 and 90 PCl5

Definition F, O, N and Cl are the