Structure of an Atom

 Number of neutrons = mass number - atomic number

 The electrostatic attraction between the positive
nucleus and negatively charged electrons orbiting around it is
what holds an atom together
 Protons, neutrons and electrons behave differently when they move
at the same velocity in an electric field
 When a beam of electrons is fired past the electrically charged
plates, the electrons are deflected very easily away from the
negative plate towards the positive plate

 This proves that the electrons are negatively charged; like

charges repel each other
 It also shows that electrons have a very small mass, as they
are easily deflected

 A beam of protons is deflected away from the positive plate and

towards the negative plate

 This proves that the proton is positively charged

 As protons are deflected less than electrons, this also shows
that protons are heavier than electrons

 A beam of neutrons is not deflected at all

 Which proves that the particle is neutral in character; it is not

attracted to, or repelled by, the negative or positive plate

 An atom is neutral and has no overall charge

 Ions on the other hand are formed when atoms
either gain or lose electrons, causing them to become charged

 Mass number = number of protons + number of neutrons

 Number of protons = mass number - number of neutrons
 An atom is neutral and therefore has the same number
of protons and electrons
 Ions have a different number of electrons to their atomic number
depending on their charge

 A positively charged ion has lost electrons and therefore

has fewer electrons than protons
 A negatively charged ion has gained electrons and therefore
has more electrons than protons
 The mass and atomic numbers can be used to find the number
of neutrons in ions and atoms:

 The atomic radius of an element is a measure of the size of an atom

 The atomic radius of an element is a measure of the size of an atom

 It is half the distance between the two nuclei of two covalently
bonded atoms of the same type
 Atomic radii show predictable patterns across the Periodic Table

 They generally decrease across each Period

 They generally increase down each Group
 The ionic radius of an element is a measure of the size of an ion

 Ionic radii show predictable patterns

 Ionic radii increase with increasing negative charge

 Ionic radii decrease with increasing positive charge

 Isotopes are atoms of the same element that contain the same number
of protons and electrons but a different number of neutrons
 The symbol for an isotope is the chemical symbol (or word) followed
by a dash and then the mass number
  Eg. carbon-12 and carbon-14 are isotopes of carbon containing 6
and 8 neutrons respectively

 Isotopes have similar chemical properties but different physical

properties

Chemical properties

 Isotopes of the same element display the same chemical

characteristics
 This is because they have the same number of electrons in
their outer shells
 Electrons take part in chemical reactions and therefore determine
the chemistry of an atom

Physical properties

 The only difference between isotopes is the number of neutrons

 Since these are neutral subatomic particles, they only add mass to the
atom
 As a result of this, isotopes have different physical properties such as
small differences in their mass and density
 The arrangement of electrons in an atom is called
the electronic configuration
 Electrons are arranged around the nucleus in principal energy
levels or principal quantum shells
 The principal quantum shells are split into subshells which are given the
letters s, p and d

 Elements with more than 57 electrons also have an f shell

 The energy of the electrons in the subshells increases in the order
s<p<d
 The order of subshells appear to overlap for the higher principal
quantum shells.
 Subshells contain one or more atomic orbitals
 Orbitals exist at specific energy levels and electrons can only be found
at these specific levels, not in between them

 Each atomic orbital can be occupied by a maximum of two

electrons

 This means that the number of orbitals in each subshell is as follows:

 s : one orbital (1 x 2 = total of 2 electrons)

 p : three orbitals ( 3 x 2 = total of 6 electrons)
 d : five orbitals (5 x 2 = total of 10 electrons)
 f : seven orbitals (7 x 2 = total of 14 electrons)
 The orbitals have specific 3-D shapes

 The ground state is the most stable electronic configuration of an

atom which has the lowest amount of energy
 This is achieved by filling the subshells of energy with the lowest energy
first (1s)
 The order of the subshells in terms of increasing energy does not follow
a regular pattern at n= 3 and higher
 Each subshell can hold a specific number of orbitals:

 s subshell : 1 orbital
 p subshell : 3 orbitals labelled px, py and pz
 d subshell : 5 orbitals
 f subshell : 7 orbitals
 All the orbitals in the same subshell have the same energy and are said
to be degenerate
 E.g. px, py and pz are all equal in energy
 The s orbitals are spherical in shape
 The p orbitals are dumbbell-shaped
 The electron configuration gives information about the number of
electrons in each shell, subshell and orbital of an atom
 Electrons with similar spin repel each other which is also called spin-
pair repulsion
 Electrons will therefore occupy separate orbitals in the same subshell to
minimize this repulsion and have their spin in the same direction
 Eg. if there are three electrons in a p subshell, one electron will go
into each px, py and pz orbital
 A free radical is a species with one or more unpaired electron
 The unpaired electron in the free radical is shown as a dot
 The Periodic Table is split up into four main blocks depending on their
electronic configuration:
 s block elements
 Have their valence electron(s) in an s orbital
 p block elements
 Have their valence electron(s) in a p orbital
 d block elements
 Have their valence electron(s) in a d orbital
 f block elements
 Have their valence electron(s) in an f orbital
Exceptions

 Chromium and copper have the following electron configurations, which

are different to what you may expect:

 Cr is [Ar] 3d5 4s1 not [Ar] 3d4 4s2

 Cu is [Ar] 3d10 4s1 not [Ar] 3d9 4s2

 This is because the [Ar] 3d5 4s1 and [Ar] 3d10 4s1 configurations
are energetically stable
 The Ionisation Energy (IE) of an element is the amount of energy
required to remove one mole of electrons from one mole of gaseous
atoms of an element to form one mole of gaseous ions
 Ionisation energies are measured under standard conditions which are
298 K and 101 kPa

 The first ionisation energy (IE1) is the energy required to remove one
mole of electrons from one mole of atoms of an element to form one
mole of 1+ ions
 Ionisation energies show periodicity - a trend across a period of the
Periodic Table
 As could be expected from their electron configuration, the group 1
metals have a relatively low ionisation energy, whereas the noble gases
have very high ionisation energies
 The size of the first ionisation energy is affected by four factors:

 Size of the nuclear charge

 Distance of outer electrons from the nucleus
 Shielding effect of inner electrons
 Spin-pair repulsion

 First ionisation energy increases across a period and decreases down a

group
 The ionisation energy across a period generally increases due to the
following factors:

 Across a period the nuclear charge increases

 This causes the atomic radius of the atoms to decrease, as the
outer shell is pulled closer to the nucleus, so the distance between
the nucleus and the outer electrons decreases
 The shielding by inner shell electrons remain reasonably constant
as electrons are being added to the same shell
 It becomes harder to remove an electron as you move across a
period; more energy is needed
 So, the ionisation energy increases
 There is a slight decrease in IE1 between beryllium and boron as the
fifth electron in boron is in the 2p subshell, which is further away from
the nucleus than the 2s subshell of beryllium
 There is a slight decrease in IE1 between nitrogen and oxygen due
to spin-pair repulsion in the 2px orbital of oxygen
 There is a large decrease in ionisation energy between the last element
in one period, and the first element in the next period
 This is because:
 There is increased distance between the nucleus and the outer
electrons as you have added a new shell
 There is increased shielding by inner electrons because of the
added shell
 These two factors outweigh the increased nuclear charge
 The ionisation energy down a group decreases due to the following
factors:
 The number of protons in the atom is increased, so the nuclear
charge increases
 But, the atomic radius of the atoms increases as you are adding
more shells of electrons, making the atoms bigger
 So, the distance between the nucleus and outer
electron increases as you descend the group
 The shielding by inner shell electrons increases as there are more
shells of electrons
 These factors outweigh the increased nuclear charge, meaning it
becomes easier to remove the outer electron as you descend a
group
 So, the ionisation energy decreases
 Energy is required to remove an outer shell electron as this involves
breaking the attractive forces between the electron and
the positively charged nucleus
 Atoms, Molecules & Stoichiometry
 The mass of a single atom is so small that it is impossible to weigh it
directly
 Atomic masses are therefore defined in terms of a standard atom which
is called the unified atomic mass unit
 This unified atomic mass is defined as one-twelfth of the mass of a
carbon-12 isotope
 The symbol for the unified atomic mass is u (often Da, Dalton, is used as
well)
 1 u = 1.66 x 10-27 kg
 The relative atomic mass (Ar) of an element is the ratio of the average
mass of the atoms of an element to the unified atomic mass unit
 The relative atomic mass is determined by using the average mass of
the isotopes of a particular element
 The Ar has no units as it is a ratio and the units cancel each other out
 The relative isotopic mass is the mass of a particular atom of
an isotope compared to the value of the unified atomic mass unit
 The relative molecular mass (Mr) is the ratio of weighted average mass
of a molecule of a molecular compound to
the unified atomic mass unit
 The relative formula mass (Mr) is used for compounds containing ions
 It has the same units and is calculated in the same way as
the relative molecular mass
 The Avogadro constant (NA or L) is the number of particles equivalent
to the relative atomic mass or molecular mass of a substance
 The value of NA is 6.02 x 1023 g mol-1
 One mole of any element is equal to the relative atomic mass of that
element in grams
 One mole of carbon, that is if you had 6.02 x 1023 atoms of carbon in your
hand, would have a mass of 12 g
  Ionic compounds are formed from a metal and a nonmetal bonded
together
 Ionic compounds are electrically neutral; the positive charges equal the
negative charges

 All metals form positive ions

 The non-metals in group 15 to 17 have a negative charge and have the
suffix ‘ide’

 Eg. nitride, chloride, bromide, iodide

Balancing equations

 During chemical reactions, atoms cannot be created or destroyed

 The number of each atom on each side of the reaction must therefore
be the same
 When balancing equations follow the following the steps:

 Write the formulae of the reactants and products

 Count the numbers of atoms in each reactant and product
 Balance the atoms one at a time until all the atoms are balanced
 Use appropriate state symbols in the equation

 The physical state of reactants and products in a chemical reaction is

specified by using state symbols

 (s) solid
 (l) liquid
 (g) gas
 (aq) aqueous

Ionic equations

 In aqueous solutions ionic compounds dissociate into their ions

 Many chemical reactions in aqueous solutions involve ionic compounds,
however only some of the ions in solution take part in the reactions
 The ions that do not take part in the reaction are called spectator ions
  An ionic equation shows only the ions or other particles taking part in
a reaction, without showing the spectator ions

Step 1: Write out the symbol equation showing reactants and products

Mg + O2 → MgO

Step 2: Count the numbers of atoms in each reactant and product

Step 3: Balance the atoms one at a time until all the atoms are balanced

2Mg + O2 → 2MgO

 This is now showing that 2 moles of magnesium react with 1 mole of

oxygen to form 2 moles of magnesium oxide
 Step 4: Use appropriate state symbols in the fully balanced equation
 2Mg(s) + O2(g) → 2MgO(s)
 The molecular formula is the formula that shows
the number and type of each atom in a molecule

 Eg. the molecular formula of ethanoic acid is C2H4O2

 The empirical formula is the simplest whole number ratio of the

elements present in one molecule or formula unit of the compound

 Eg. the empirical formula of ethanoic acid is CH2O

 Water of crystallisation is when some compounds can
form crystals which have water as part of their structure
 A compound that contains water of crystallisation is called a hydrated
compound
 A compound which doesn’t contain water of crystallisation is called
an anhydrous compound

 E.g. hydrated copper(II) sulfate is CuSO4∙5H2O

 E.g. anhydrous copper(II) sulfate is CuSO4

 A compound can be hydrated to different degrees

 E.g. cobalt(II) chloride can be hydrated by six or two water

molecules
 CoCl2 ∙6H2O or CoCl2 ∙2H2O
 The degree of hydration can be calculated from experimental results:
 The mass of the hydrated salt must be measured before heating
 The salt is then heated until it reaches a constant mass
 The two mass values can be used to calculate the number of
moles of water in the hydrated salt - known as the water of
crystallisation
 10.0 g of hydrated copper sulfate are heated to a constant mass of 5.59
g. Calculate the formula of the original hydrated copper sulfate.

(Mr data: CuSO4 = 159.6, H2O = 18.0)

 The number of moles of a substance can be found by using the

following equation:

 The masses of reactants are useful to determine how much of the

reactants exactly react with each other to prevent waste
 To calculate the reacting masses, the chemical equation is required
 This equation shows the ratio of moles of all the reactants and products,
also called the stoichiometry, of the equation
 To find the mass of products formed in a reaction the following pieces
of information is needed:

 The mass of the reactants

 The molar mass of the reactants
 The balanced equation
 In a lot of reactions, not all reactants react to form products which can
be due to several factors:
 Other reactions take place simultaneously
 The reaction does not go to completion
 Reactants or products are lost to the atmosphere
 The percentage yield shows how much of a particular product you get
from the reactants compared to the maximum theoretical amount that
you can get:
 
Step 1: The symbol equation is:

2Mg(s) + O2(g) → 2MgO(s)

 Step 2: The relative formula masses are:

Magnesium : 24 Oxygen : 32 Magnesium Oxide : 40

 Step 3: Calculate the moles of magnesium used in reaction

 Step 4: Find the ratio of magnesium to magnesium oxide using the

balanced chemical equation

Therefore, 0.25 mol of MgO is formed

 Step 5: Find the mass of magnesium oxide

mass = mol x Mr

mass = 0.25 mol x 40 g mol-1

mass = 10 g

Therefore, mass of magnesium oxide produced is 10 g

 Sometimes, there is an excess of one or more of the reactants (excess
reagent)
 The reactant which is not in excess is called the limiting reagent
 To determine which reactant is limiting:

 The number of moles of the reactants should be calculated

 The ratio of the reactants shown in the equation should be taken
into account

 Avogadro suggested that ‘equal volumes of gases contain the same

number of molecules’ (also called Avogadro’s hypothesis)
 At room temperature (20 degrees Celsius) and pressure (1 atm) one
mole of any gas has a volume of 24.0 dm3
 This molar gas volume of 24.0 dm3 can be used to find:
o The volume of a given mass or number of moles of gas:

volume of gas (dm3) = amount of gas (mol) x 24

 The mass or number of moles of a given volume of gas:

 The concentration of a solution is the amount of solute dissolved in

a solvent to make 1 dm3 of solution
o The solute is the substance that dissolves in a solvent to form a
solution
o The solvent is often water

 A concentrated solution is a solution that has a high concentration of

solute
 A dilute solution is a solution with a low concentration of solute
 When carrying out calculations involve concentrations in mol dm-3 the
following points need to be considered:
  Change mass in grams to moles
 Change cm3 to dm3

 To calculate the mass of a substance present in solution of

known concentration and volume:

 Rearrange the concentration equation

number of moles (mol) = concentration (mol dm-3) x volume (dm3)

 Multiply the moles of solute by its molar mass

mass of solute (g) = number of moles (mol) x molar mass (g mol-1)

 The stoichiometry of a reaction can be found if the exact amounts of

reactants and products formed are known
 The amounts can be found by using the following equation:

 Electronegativity is the ability of an atom to attract a pair of electrons

towards itself in a covalent bond
 This phenomenon arises from the positive nucleus’s ability to attract
the negatively charged electrons, in the outer shells, towards itself
Electronegativity: Affecting Factors
Nuclear charge

 Attraction exists between the positively charged protons in the nucleus

and negatively charged electrons found in the energy levels of an atom
 An increase in the number of protons leads to
an increase in nuclear attraction for the electrons in the outer shells
 Therefore, an increased nuclear charge results in an increased
electronegativity

As the nuclear charge increases, the electronegativity of an element

increases as well

Atomic radius

 The atomic radius is the distance between the nucleus and electrons in
the outermost shell
 Electrons closer to the nucleus are more strongly attracted towards its
positive nucleus
 Those electrons further away from the nucleus are less
strongly attracted towards the nucleus
 Therefore, an increased atomic radius results in a decreased
electronegativity

As the atomic radius increases, the nucleus has less of an attraction for
the bonding electrons causing atom A to have a higher electronegativity
than atom B

Shielding

 Filled energy levels can shield (mask) the effect of the nuclear charge
causing the outer electrons to be less attracted to the nucleus
 Therefore, the addition of extra shells and subshells in an atom will
cause the outer electrons to experience less of the attractive force of the
nucleus

 Sodium (Period 3, Group 1) has higher electronegativity than

caesium (Period 6, Group 1) as it has fewer shells and therefore
the outer electrons experience less shielding than in caesium

 Thus, an increased number of inner shells and subshells will result in

a decreased electronegativity

Filled inner energy levels mask the nuclear attraction from the outer
bonding electrons
  Electronegativity varies across Periods and down the Groups of the
Periodic Table

Down a group

 There is a decrease in electronegativity going down the Group

 The nuclear charge increases as more protons are being added to the
nucleus
 However, each element has an extra filled electron shell, which
increases shielding
 The addition of the extra shells increases the distance between the
nucleus and the outer electrons resulting in larger atomic radii
 Overall, there is decrease in attraction between the nucleus and outer
bonding electrons

Electronegativity decreases going down the groups of the periodic table

Across a period

 Electronegativity increases across a Period

  The nuclear charge increases with the addition of protons to the
nucleus
 Shielding remains reasonably the same across the Period as no new
shells are being added to the atoms
 The nucleus has an increasingly strong attraction for the bonding pair of
electrons of atoms across the Period of the Periodic Table
 This results in smaller atomic radii

Electronegativity increases going across the periods of the Periodic Table

Trends down a group & across a period table

  The differences in Pauling electronegativity values can be used to
predict whether a bond is covalent or ionic in character

Electronegativity & covalent bonds

 Single covalent bonds are formed by sharing a pair of electrons

between two atoms
 In diatomic molecules the electron density is shared equally between
the two atoms
o Eg. H2, O2 and Cl2
 Both atoms will have the same electronegativity value and have
an equal attraction for the bonding pair of electrons leading to
formation of a covalent bond
 The equal distribution leads to a non-polar molecule

The electronegativity values are equal resulting in the formation of a

nonpolar covalent bond

Electronegativity & ionic bonds

 When atoms of different electronegativities form a molecule, the

shared electrons are not equally distributed in the bond
 The more electronegative atom (the atom with the higher value on the
Pauling scale) will draw the bonding pair of electrons towards itself
 A molecule with partial charges forms as a result
 The more electronegative atom will have a partial negative charge
(delta negative, δ-)
 The less electronegative atom will have a partial positive charge (delta
positive, δ+)
 This leads to a polar covalent molecule

The electronegativity values are not equal - polar bond forms

 If there is a large difference in electronegativity of the two atoms in a

molecule, the least electronegative atom’s electron will transfer to the
other atom
 This in turn leads to an ionic bond – one atom transfers its electron and
the other gains that electron
o The cation is a positively charged species which has lost (an)
electron(s)
o The anion is a negatively charged species which has gained (an)
electron(s)
 As a general rule, metals are on the left of the Periodic Table
and nonmetals are on the right-hand side
 Ionic bonding involves the transfer of electrons from
a metallic element to a non-metallic element
 Transferring electrons usually leaves the metal and the non-metal with
a full outer shell
 Metals lose electrons from their valence shell forming positively
charged cations
 Non-metal atoms gain electrons forming negatively charged anions
 Once the atoms become ions, their electronic configurations are the
same as a stable noble gas.
 Cations and anions are oppositely charged and therefore attracted to
each other
 Electrostatic attractions are formed between the oppositely charged
ions to form ionic compounds
 The ionic bond is the electrostatic attraction formed between the
oppositely charged ions, which occurs in all directions
 This form of attraction is very strong and requires a lot of energy to
overcome

 This causes high melting points in ionic compounds

 The ions form a lattice structure which is an evenly
distributed crystalline structure
 Ions in a lattice are arranged in a regular repeating pattern so that
positive charges cancel out negative charges
 The attraction between the cations and anions is occurring in all
directions
 Each ion is attracted to all of the oppositely charged ions around
it
 Therefore the final lattice is overall electrically neutral
 Metal atoms are tightly packed together in lattice structures
 When the metal atoms are in lattice structures, the electrons in their
outer shells are free to move throughout the structure
 The free-moving electrons are called ‘delocalised electrons’ and they
are not bound to their atom
 When the electrons are delocalised, the metal atoms
become positively charged
 The positive charges repel each other and keep the neatly arranged
lattice in place
 There are very strong forces between the positive metal centres and the
‘sea’ of delocalised electrons
 Covalent bonding occurs between two nonmetals
 A covalent bond involves the electrostatic attraction between nuclei of
two atoms and the bonding electrons of their outer shells
 No electrons are transferred but only shared in this type of bonding
 Non-metals are able to share pairs of electrons to form different types
of covalent bonds
 Sharing electrons in the covalent bond allows each of the 2 atoms to
achieve an electron configuration similar to a noble gas
 This makes each atom more stable
 Dot and cross diagrams are used to represent covalent bonding
 They show just the outer shell of the atoms involved
 To differentiate between the two atoms involved, dots for electrons of
one atom and crosses for electrons of the other atom are used
 Electrons are shown in pairs on dot-and-cross diagrams
 In simple covalent bonds the two atoms involved shares electrons
 Some molecules have a lone pair of electrons that can be donated to
form a bond with an electron-deficient atom
 An electron-deficient atom is an atom that has an unfilled outer
orbital
 So both electrons are from the same atom
 This type of bonding is called dative covalent bonding or coordinate
bond
 An example of a dative bond is in an ammonium ion
 The hydrogen ion, H+ is electron-deficient and has space for two
electrons in its shell
 The nitrogen atom in ammonia has a lone pair of electrons which
it can donate to the hydrogen ion to form a dative covalent bond
Ammonia (NH3) can donate a lone pair to an electron-deficient proton
(H+) to form a charged ammonium ion (NH4+)
Bond overlap in covalent bonds

 A single covalent bond is formed when two nonmetals combine

 Each atom that combines has an atomic orbital containing a single
unpaired electron
 When a covalent bond is formed, the atomic orbitals overlap to form
a combined orbital containing two electrons
o This new orbital is called the molecular orbital
 The greater the atomic orbital overlap, the stronger the bond
 Sigma (σ) bonds are formed by direct overlap of orbitals between the
bonding atoms
 Pi (π) bonds are formed by the sideways overlap of adjacent above
and below the σ bond

σ bonds

 Sigma (σ) bonds are formed from the end-on overlap of atomic
orbitals
 S orbitals overlap this way as well as p orbitals

Sigma orbitals can be formed from the end-on overlap of s orbitals

 The electron density in a σ bond is symmetrical about a line joining the

nuclei of the atoms forming the bond
 The pair of electrons is found between the nuclei of the two atoms
 The electrostatic attraction between the electrons and nuclei bonds the
atoms to each other
π bonds

 Pi (π) bonds are formed from the sideways overlap of adjacent p

orbitals
 The two lobes that make up the π bond
lie above and below the plane of the σ bond
 This maximises overlap of the p orbitals
 A single π bond is drawn as two electron clouds one arising from each
lobe of the p orbitals
 The two clouds of electrons in a π bond represent one bond
containing two electrons

π orbitals can be formed from the end-on overlap of p orbitals

Examples of sigma & pi bonds

 Hydrogen

 The hydrogen atom has only one s orbital

 The s orbitals of the two hydrogen atoms will overlap to form a σ
bond
Direct overlap of the 1s orbitals of the hydrogen atoms results in the
formation of a σ bond

 The p atomic orbitals can also overlap end-on to form σ bonds

 In order for them to do this, they first need to become modified in
order to gain s orbital character
 The orbitals are therefore slightly changed in shape to make one of the
p orbital lobes bigger
 This mixing of atomic orbitals to form covalent bonds is
called hybridisation
o Mixing one s orbital with three p orbitals is
called sp3 hybridisation (each orbital has ¼ s character and ¾ p
character)
o Mixing one s orbital with two p orbitals is called sp2 hybridisation
o Mixing one s orbital with one p orbital
forms sp hybridised orbitals
π orbitals can be formed from the end-on overlap of p orbitals
The mixing of s orbitals with p orbitals to form molecular bonds is called
hybridisation
Bond energy

 The bond energy is the energy required to break one mole of a

particular covalent bond in the gaseous states
o Bond energy has units of kJ mol-1
 The larger the bond energy, the stronger the covalent bond is

Bond length

 The bond length is internuclear distance of two covalently bonded

atoms
o It is the distance from the nucleus of one atom to another atom
which forms the covalent bond
 The greater the forces of attraction between electrons and nuclei, the
more the atoms are pulled closer to each other
 This decreases the bond length of a molecule
and increases the strength of the covalent bond
 Triple bonds are the shortest and strongest covalent bonds due to the
large electron density between the nuclei of the two atoms
 This increase the forces of attraction between the electrons and nuclei of
the atoms
 As a result of this, the atoms are pulled closer together causing a shorter
bond length
 The increased forces of attraction also means that the covalent bond
is stronger
 The reactivity of a covalent bond is greatly influenced by:

 The bond polarity

 The bond strength
 The bond type (σ/π)

 The valence shell electron pair repulsion theory (VSEPR) predicts the
shape and bond angles of molecules
 Electrons are negatively charged and will repel other electrons when
close to each other
  In a molecule, the bonding pair of electrons will repel other electrons
around the central atom forcing the molecule to adopt a shape in
which these repulsive forces are minimised
 When determining the shape and bond angles of a molecule, the
following VSEPR rules should be considered:

 Valence shell electrons are those electrons that are found in the
outer shell
 Electron pairs repel each other as they have similar charges
 Lone pair electrons repel each other more than bonded pairs
 Repulsion between multiple and single bonds is treated the same
as for repulsion between single bonds
 Repulsion between pairs of double bonds are greater
 The most stable shape is adopted to minimize the repulsion forces

 Different types of electron pairs have different repulsive forces

 Lone pairs of electrons have a more concentrated electron charge

cloud than bonding pairs of electrons
 The cloud charges are wider and closer to the central atom’s
nucleus
 The order of repulsion is therefore: lone pair – lone pair > lone
pair – bond pair > bond pair – bond pair

 Tip: A lone pair adds decrease bond angle by 2.5

Hydrogen bonding

 Hydrogen bonding is the strongest form of intermolecular bonding

 Intermolecular bonds are bonds between molecules

 Hydrogen bonding is a type of permanent dipole – permanent
dipole bonding

 For hydrogen bonding to take place the following is needed:

 A species which has an O or N (very electronegative) atom with

an available lone pair of electrons
  A species with an -OH or -NH group

 When hydrogen is covalently bonded to an electronegative atom, such

as O or N, the bond becomes very highly polarised
 The H becomes so δ+ charged that it can form a bond with the lone
pair of an O or N atom in another molecule

 For hydrogen bonding to take place, the angle between the -OH/-
NH and the hydrogen bond is 180o
 The number of hydrogen bonds depends on:

 The number of hydrogen atoms attached to O or N in the

molecule
 The number of lone pairs on the O or N

Water can form a maximum of two hydrogen bonds per molecule

Properties of water

 Hydrogen bonding in water, causes it to have anomalous

properties such as high melting and boiling points, high surface tension
and anomalous density of ice compared to water

High melting & boiling points

 Water has high melting and boiling points which is caused by

the strong intermolecular forces of hydrogen bonding between the
molecules
 In ice (solid H2O) and water (liquid H2O) the molecules are tightly held
together by hydrogen bonds
 A lot of energy is therefore required to break the water molecules apart
and melt or boil them
  The graph above compares the enthalpy of vaporisation (energy
required to boil a substance) of different hydrides
 The enthalpy changes increase going from H2S to H2Te due to the
increased number of electrons in the Group 16 elements
 This causes an increased instantaneous dipole - induced dipole
forces as the molecules become larger
 Based on this, H2O would have a much lower enthalpy change (around
17 kJ mol-1)
 However, the enthalpy change of vaporisation is almost 3
times larger which is caused by the hydrogen bonds present in water
but not in the other hydrides

The high enthalpy change of evaporation of water suggests that

instantaneous dipole-induced dipole forces are not the only forces present
in the molecule – there are also those of the strong hydrogen bonds,
which cause the high boiling points

High surface tension

 Water has a high surface tension

 Surface tension is the ability of a liquid surface to resist any external
forces (i.e. to stay unaffected by forces acting on the surface)
  The water molecules at the surface of liquid are bonded to other water
molecules through hydrogen bonds
 These molecules pull downwards on the surface molecules causing
the surface them to become compressed and more tightly together at
the surface
 This increases water’s surface tension

The surface molecules are pulled downwards due to the hydrogen bonds
with other molecules, whereas the inner water molecules are pulled in all
directions

Density

 Solids are denser than their liquids as the particles in solids are
more closely packed together than in their liquid state
 In ice however, the water molecules are packed in a 3D hydrogen-
bonded network in a rigid lattice
 Each oxygen atom is surrounded by hydrogen atoms
 This way of packing the molecules in a solid and the relatively
long bond lengths of the hydrogen bonds means that the water
molecules are slightly further apart than in the liquid form
 Therefore, ice has a lower density than liquid water

The ‘more open’ structure of molecules in ice causes it to have a lower

density than liquid water
  Electronegativity is the ability of an atom to draw a pair of electrons
towards itself in a covalent bond
 Electronegativity increases across a Period and decreases going down a
Group

Polarity

 When two atoms in a covalent bond have the same

electronegativity the covalent bond is nonpolar
 When two atoms in a covalent bond have different
electronegativities the covalent bond is polar and the electrons will be
drawn towards the more electronegative atom
 As a result of this:
o The negative charge centre and positive charge centre do
not coincide with each other
o This means that the electron distribution is asymmetric
o The less electronegative atom gets a partial charge of δ+
(delta positive)
o The more electronegative atom gets a partial charge of δ-
(delta negative)
 The greater the difference in electronegativity the more polar the bond
becomes

 The dipole moment is a measure of how polar a bond is

 The direction of the dipole moment is shown by the following sign in
which the arrow points to the partially negatively charged end of the
dipole:
Assigning polarity to molecules

 To determine whether a molecule with more than two atoms is polar,

the following things have to be taken into consideration:

 The polarity of each bond

 How the bonds are arranged in the molecule

 Some molecules have polar bonds but are overall not polar because
the polar bonds in the molecule are arranged in such way that the
individual dipole moments cancel each other out

 Covalent bonds are strong intramolecular forces

 Molecules also contain weaker intermolecular forces which are
forces between molecules
 These intermolecular forces are called van der Waals’ forces
 There are two types of van der Waals’ forces:

 Instantaneous (temporary) dipole – induced dipole forces also

called London dispersion forces
 Permanent dipole – permanent dipole forces

Instantaneous dipole - induced dipole (id - id)

 Instantaneous dipole - induced dipole forces or London dispersion

forces exist between all atoms or molecules
 The electron charge cloud in non-polar molecules or atoms are
constantly moving
 During this movement, the electron charge cloud can be more on one
side of the atom or molecule than the other
 This causes a temporary dipole to arise
 This temporary dipole can induce a dipole on neighbouring molecules
 When this happens, the δ+ end of the dipole in one molecule and
the δ- end of the dipole in a neighbouring molecule
are attracted towards each other
  Because the electron clouds are moving constantly, the dipoles are
only temporary
 Id - id forces increase with:

 Increasing number of electrons (and atomic number) in the

molecule
 Increasing the places where the molecules come close together

Permanent dipole - permanent dipole (pd - pd)

 Polar molecules have permanent dipoles

 The molecule will always have a negatively and positively charged end
 Forces between two molecules that have permanent dipoles are
called permanent dipole - permanent dipole forces
 The δ+ end of the dipole in one molecule and the δ- end of the
dipole in a neighbouring molecule are attracted towards each other

 For small molecules with the same number of electrons, pd - pd forces

are stronger than id – id

 Hydrogen bonding is an intermolecular force between molecules with

an -OH/-NH group and molecules with an N/O atom
 Hydrogen bonding is a special case of a permanent dipole - dipole
force between molecules
o Hydrogen bonds are stronger forces than pd - pd forces
 The hydrogen is bonded to an O/N atom which is so electronegative,
that almost all the electron density from the covalent bond is drawn
towards the O/N atom
 This leaves the H with a large delta positive and the O/N with a large
delta negative charging resulting in the formation of a permanent
dipole in the molecule
 A delta positive H in one molecule is electrostatically attracted to
the delta negative O/N in a neighbouring molecule
Intramolecular forces

 Intramolecular forces are forces within a molecule

 Ionic bonding is the electrostatic
attraction between positive (cations) and negative (anions) ions in an
ionic crystal lattice
o These ions are formed by transferring the electrons from one
species to the other
 Covalent bonds are formed when the outer electrons of two atoms
are shared
 Metallic bonding is the electrostatic attraction of positively charged
metal ions and their delocalised electrons in a metal lattice

Intermolecular forces

 Intermolecular forces are forces between molecules and are also

called van der Waals’ forces
 Permanent dipole - permanent dipole are the attractive forces
between two neighbouring molecules with a permanent dipole
 Hydrogen bonds are a special type of permanent dipole - permanent
dipole forces
 Instantaneous dipole - induced dipole (London dispersion) forces are
the attractive forces between a temporary dipole and a neighbouring
molecule with an induced dipole
 In general, the intramolecular forces are stronger than intermolecular
forces
 The strengths of the types of bond or force are as follows:
States of Matter
 Gases in a container exert a pressure as the gas molecules are
constantly colliding with the wall of the container

Changing gas volume

 Decreasing the volume (at constant temperature) of the container

causes the molecules to be squashed together which results in
more frequent collisions with the container wall
 The pressure of the gas increases
 The volume is therefore inversely proportional to the pressure (at
constant temperature)

 A graph of volume of gas plotted against 1/pressure gives a

straight line

Changing gas temperature

 Increasing the temperature (at constant volume) of the gas causes the
molecules to gain more kinetic energy
 This means that the particles will move faster and collide with the
container walls more frequently
 The pressure of the gas increases
 The temperature is therefore directly proportional to the pressure (at
constant volume)

 A graph of temperature of gas plotted against pressure gives a

straight line

Kinetic theory of gases

 The kinetic theory of gases states that molecules in gases are

constantly moving
 The theory makes the following assumptions:

 The gas molecules are moving very fast and randomly

  The molecules hardly have any volume
 The gas molecules do not attract or repel each other
(no intermolecular forces)
 No kinetic energy is lost when the gas molecules collide with each
other (elastic collisions)
 The temperature of the gas is related to the average kinetic
energy of the molecules

 Gases that follow the kinetic theory of gases are called ideal gases
 However, in reality gases do not fit this description exactly but may
come very close and are called real gases

Ideal gases

 The volume that an ideal gas occupies depends on:

 Its pressure
 Its temperature

 When a gas is heated (at constant pressure) the particles gain

more kinetic energy and undergo more frequent collisions with the
container wall
 To keep the pressure constant, the molecules must get further apart
and therefore the volume increases
 The volume is therefore directly proportional to the temperature (at
constant pressure)
 At very high pressures and low temperatures real gases do not obey
the kinetic theory as under these conditions:

 Molecules are close to each other

 There are instantaneous dipole- induced dipole or permanent
dipole- permanent dipole forces between the molecules
 These attractive forces pull the molecules away from the container
wall
 The volume of the molecules is not negligible
 The ideal gas equation shows the relationship between pressure,
volume, temperature and number of moles of gas of an ideal gas:
 pV = nRT

p = pressure (pascals, Pa)

V = volume (m3)

n = number of moles of gas (mol)

R = gas constant (8.31 J K-1 mol-1)

T = temperature (kelvin, K)

 The ideal gas equation can also be used to calculate

the molar mass (Mr) of a gas

 The Ideal Gas Law is a simple equation demonstrating the relationship

between temperature, pressure, and volume for gases. These specific
relationships stem from Charles’s Law, Boyle’s Law, and Gay-Lussac’s
Law. Charles’s Law identifies the direct proportionality between volume
and temperature at constant pressure, Boyle’s Law identifies the inverse
proportionality of pressure and volume at a constant temperature, and
Gay-Lussac’s Law identifies the direct proportionality of pressure and
temperature at constant volume. Combined, these form the Ideal Gas
Law equation: PV = NRT. P is the pressure, V is the volume, N is the
number of moles of gas, R is the universal gas constant, and T is the
absolute temperature.
 For a gas to be “ideal” there are four governing assumptions:
 The gas particles have negligible volume.
 The gas particles are equally sized and do not have intermolecular
forces (attraction or repulsion) with other gas particles.
 The gas particles move randomly in agreement with Newton’s Laws of
Motion.
 The gas particles have perfect elastic collisions with no energy loss.
  Most ionic, metallic and covalent compounds are crystalline lattice
 The ions, atoms or molecules are arranged in a regular and repeating
arrangement

Giant ionic lattices

 An ionic bond is an electrostatic force between a positively charged

metal (cation) ion and a negatively charged non-metal (anion) ion

 The metal becomes positively charged as it transfers electrons to

the non-metal becomes negatively charged

 Ionic compounds are arranged in giant ionic lattices (also called giant
ionic structures)
 The type of lattice formed depends on the sizes of
the positive and negative ions which are arranged in
an alternating fashion

 The ionic lattice of MgO and NaCl are cubic

 Covalent bonds are bonds between nonmetals in which electrons

are shared between the atoms
 Covalent compounds can be arranged in simple molecular or giant
molecular lattices

 Simple molecular lattices: Iodine, buckminsterfullerene (C60) and

ice
 Giant molecular: silicon(IV) oxide, graphite and diamond

 Metals form giant metallic lattices in which the metal ions are
surrounded by a ‘sea’ of delocalised electrons
 The metal ions are often packed in hexagonal layers or in a cubic
arrangement
  Different types of structure and bonding have different effects on
the physical properties of substances such as
their melting and boiling points, electrical
conductivity and solubility

Ionic bonding & giant ionic lattice structures

 Ionic compounds are strong

 The strong electrostatic forces in ionic compounds keep the ions

strongly together

 They are brittle as ionic crystals can split apart

 Ionic compounds have high melting and boiling points

 The strong electrostatic forces between the ions in the lattice act
in all directions and keep them strongly together
 Melting and boiling points increase with charge density of the
ions due to the greater electrostatic attraction of charges
 Mg2+O2- has a higher melting point Na+Cl-

 Ionic compounds are soluble in water as they can form ion - dipole
bonds
 Ionic compounds only conduct electricity when molten or in solution

 When molten or in solution, the ions can freely move around and
conduct electricity
 In the solid state they’re in a fixed position and unable to move
around

Metallic bonding & giant metallic lattice structures

 Metallic compounds are malleable

 When a force is applied, the metal layers can slide

 The attractive forces between the metal ions and electrons act in
all directions
 So when the layers slide, the metallic bonds are re-formed
  The lattice is not broken and has changed shape

 Metallic compounds are strong and hard

 Due to the strong attractive forces between the metal ions and
delocalised electrons

 Metals have high melting and boiling points

 Pure metals are insoluble in water
 Metals can conduct electricity when in the solid or liquid state

 As both in the solid and liquid state there are mobile electrons which
can freely move around and conduct electricity

 Simple covalent lattices have low melting and boiling points

 These compounds have weak intermolecular forces between the

molecules
 Only little energy is required to break the lattice

 Most compounds are insoluble with water

o Unless they are polar (such as HCl) or can form hydrogen bonds
(such as NH3)
 They do not conduct electricity in the solid or liquid state as there are
no charged particles

 Some simple covalent compounds to conduct electricity in

solution such as HCl which forms H+ and Cl- ions

Covalent bonding & giant covalent lattice structures

 Giant covalent lattices have high melting and boiling points

 These compounds have a large number of covalent bonds linking

the whole structure and intermolecular forces between the
molecules
  A lot of energy is required to break the lattice

 The compounds can be hard or soft

 Graphite is soft as the forces between the carbon layers are weak
 Diamond and silicon(IV) oxide are hard as it is difficult to break
their 3D network of strong covalent bonds

 Most compounds are insoluble in water

 Most compounds do not conduct electricity however some do

 Graphite has delocalised electrons between the carbon layers

which can move along the layers when a voltage is applied
 Diamond and silicon(IV) oxide do not conduct electricity as all four
outer electrons on every carbon atom is involved in a covalent
bond so there are no free electrons available
Chemical Energetics
 The total chemical energy inside a substance is called the enthalpy (or
heat content)
 When chemical reactions take place, changes in chemical energy take
place and therefore the enthalpy changes
 An enthalpy change is represented by the symbol ΔH (Δ= change; H =
enthalpy)
 An enthalpy change can be positive or negative

Exothermic reactions

 A reaction is exothermic when the products have less energy than the
reactants
 Heat energy is given off by the reaction to the surroundings
o The temperature of the environment increases - this can be
measured on a thermometer
o The temperature of the system decreases
 There is an enthalpy decrease during the reaction so ΔH is negative
 Exothermic reactions are thermodynamically possible (because the
enthalpy of the reactants is higher than that of the products)
 However, the rate may be too slow to observe any appreciable reaction
o In this case the reaction is kinetically controlled
o This means the reaction could have a high activation energy which
is preventing the reaction from taking place.
 The enthalpy change during an exothermic reaction

Endothermic reactions

 A reaction is endothermic when the products have more energy than

the reactants
 Heat energy is absorbed by the reaction from the surroundings
o The temperature of the environment decreases - this can be
measured with a thermometer
o The temperature of the system increases
 There is an enthalpy increase during the reaction so ΔH is positive
 The enthalpy change during an endothermic reaction

 An energy level diagram is a diagram that shows the energies of the

reactants, the transition state(s) and the products of the reaction with
time
 The transition state is a stage during the reaction at which chemical
bonds are partially broken and formed
 The transition state is very unstable – it cannot be isolated and is higher
in energy than the reactants and products
 The activation energy (Ea) is the energy needed to reach the transition
state
 We can define the activation energy as ‘the minimum amount of energy
needed for reactant molecules to have a successful collision and start the
reaction’
 In an exothermic reaction, the reactants are higher in energy than the
products
 The reactants are therefore closer in energy to the transition state
 This means that exothermic reactions have a lower activation energy
compared to endothermic reactions

 In an endothermic reaction, the reactants are lower in energy than the

products
 The reactants are therefore further away in energy to the transition state
 This means that endothermic reactions have a higher activation energy
compared to exothermic reactions
 To fairly compare the changes in enthalpy between reactions, all
reactions should be carried out under standard conditions
 These standard conditions are:

 A pressure of 101 kPa

 A temperature of 298 K (25 oC)
 Each substance involved in the reaction is in its normal physical
state (solid, gas or liquid)

 To show that a reaction has been carried out under standard conditions,
the symbol Ꝋ is used

 ΔHꝊ = the standard enthalpy change

 These are a number of key definitions for common language relating to

enthalpy change that all chemists need to know
 During a reaction, enthalpy changes take place because bonds are being
broken and formed
 Energy (in the form of heat) is needed to overcome attractive forces
between atoms
 Bond breaking is therefore endothermic
 Energy is released from the reaction to the surroundings (in the form of
heat) when new bonds are formed
 Bond forming is therefore exothermic
 If more energy is required to break bonds than energy is released when
new bonds are formed, the reaction is endothermic
 If more energy is released when new bonds are formed than energy is
required to break bonds, the reaction is exothermic
 In reality, only some bonds in the reactants are broken and then new
ones are formed
 The amount of energy required to break one mole of a specific covalent
bond in the gas phase is called the bond dissociation energy
 Bond dissociation energy (E) is also known as exact bond
energy or bond enthalpy
 The type of bond broken is put in brackets after E

 Eg. EE(H-H) is the bond energy of a mole of single bonds between

two hydrogen atoms
 Bond energies are affected by other atoms in the molecule (the
environment)
 Therefore, an average of a number of the same type of bond but in
different environments is calculated
 This bond energy is known as the average bond energy
 Since bond energies cannot be determined directly, enthalpy cycles are
used to calculate the average bond energy
Calculating enthalpy change from bond energies

 Bond energies are used to find the ΔHrꝋ of a reaction when this cannot
be done experimentally
 Eg. the Haber Process

Measuring enthalpy changes

 Calorimetry is a technique used to measure changes in enthalpy of

chemical reactions
 A calorimeter can be made up of a polystyrene drinking cup,
a vacuum flask or metal can

A polystyrene cup can act as a calorimeter to find enthalpy changes in a

chemical reaction
  The energy needed to increase the temperature of 1 g of a substance by
1 oC is called the specific heat capacity (c) of the liquid
 The specific heat capacity of water is 4.18 J g-1 oC-1
 The energy transferred as heat can be calculated by:

Hess Cycles

 Hess’s Law states that:

"The total enthalpy change in a chemical reaction is independent of

the route by which the chemical reaction takes place as long as the
initial and final conditions are the same."

 This means that whether the reaction takes place in one or two steps,
the total enthalpy change of the reaction will still be the same
Calculating ΔHr from ΔHf using Hess’s Law energy cycles

 The products can be directly formed from the elements = ΔH2

OR

 The products can be indirectly formed from the elements = ΔH1 + ΔHr

The enthalpy change from elements to products (direct route) is equal to

the enthalpy change of elements forming reactants and then products
(indirect route)

 Equation

ΔH2 = ΔH1 + ΔHr

Therefore,

ΔHr = ΔH2 – ΔH1

 Step 1: Write the balanced equation at the top

 Step 2: Draw the cycle with the elements at the bottom

  Step 3: Draw in all arrows, making sure they go in the correct directions.
Write the standard enthalpy of formations

 Step 4: Apply Hess’s Law

Calculating ΔHf from ΔHc using Hess’s Law energy cycles

 The combustion products can be formed directly from elements to

combustion products = ΔH1

OR

 The combustion products can be formed indirectly from elements to

compound to combustion products = ΔHf+ ΔH2
 The enthalpy change going from elements to products (direct route) is
equal to the enthalpy change of elements forming reactants and then
products (indirect route)

 Equation

ΔH1 = ΔHf + ΔH2

Therefore,

ΔHf = ΔH1 – ΔH2

Electrochemistry
 The oxidation numbers (also known as oxidation state) is a number
given to each atom or ion in a compound to keep track of how many
electrons they have
 In a single ion or molecular ion, the oxidation number tells us how many
electrons have been lost or gained
 Positive oxidation number = loss of electrons
 Negative oxidation number = gain of electrons

Oxidation number rules

 The oxidation number (ox.no.) refers to a single atom in a compound

 Oxidation numbers can be used to balance chemical equations
 Roman numerals between brackets are used to show the ox. no. of an
atom that can have multiple oxidation states

 Step 1: Write the unbalanced equation and identify the atoms which
change in ox. no.

 Step 2: Deduce the ox.no. changes

 Step 3: Balance the ox.no. changes

 Step 4: Balance the charges

 Step 5: Balance the atoms

Oxidation

 Oxidation is the gain of oxygen,

 Oxidation is also the loss of a hydrogen
 Oxidation is also the loss of electrons

 Oxidation causes an increase in ox. No

 Reduction

 Reduction is the loss of oxygen,

 Reduction is also the gain of a hydrogen
 Reduction is also the gain of electrons
 Reduction causes a decrease in oxidation number,

Use the acronym "Oil Rig" to help you remember the definitions of
oxidation and reduction

Redox reactions

 Redox reactions are reactions in which oxidation and reduction take

place together
 While one species is oxidising, another is reducing in the same reaction

Cu2++ Mg → Mg2+ + Cu

(Cu has been reduced and Mg has been oxidised)

Disproportionation reactions

 A disproportionation reaction is a reaction in which the same species

is both oxidised and reduced

Example of a disproportion reaction in which the same species (chlorine

in this case) has been both oxidised and reduced

Oxidising agent

 An oxidising agent is a substance that oxidises another atom or ion by

causing it to lose electrons
 An oxidising agent itself gets reduced – gains electrons
 Therefore, the ox. no. of the oxidising agent decreases

Example of an oxidising agent in a chemical reaction

Reducing agent

 A reducing agent is a substance that reduces another atom or ion by

causing it to gain electrons
 A reducing agent itself gets oxidised – loses/donates electrons
 Therefore, the ox. no. of the reducing agent increases

Example of a reducing agent in a chemical reaction

 For a reaction to be recognised as a redox reaction, there must be both

an oxidising and reducing agent
 Some substances can act both as oxidising and reducing agents
 Their nature is dependent upon what they are reacting with and the
reaction conditions

Roman numerals

 Roman numerals are used to show the oxidation states of transition

metals which can have more than one oxidation number
 Iron can be both +2 and +3 so Roman numerals are used to distinguish
between them

 Fe2+ in FeO can be written as Iron(II) oxide

 Fe3+ in Fe2O3 can be written as Iron(III) oxide
Chemical Equilibria
Reversible reaction

 Some reactions go to completion where the reactants are used up to

form the products and the reaction stops when all of the reactants are
used up
 In reversible reactions the products can react to reform the original
reactants
 To show a reversible reaction, two opposing half arrows are used: ⇌

The diagram shows an example of a forward and backward reaction that

can be written as one equation using two half arrows

Dynamic equilibrium

 In a dynamic equilibrium the reactants and products

are dynamic (they are constantly moving)
 In a dynamic equilibrium the rate of the forward reaction is the same as
the rate of the backward reaction in a closed system, and
the concentrations of the reactants and products is constant\
 A closed system is one in which none of the reactants or products
escape from the reaction mixture
  In an open system, matter and energy can be lost to the surroundings
 When a reaction takes place entirely in solution, equilibrium can be
reached in open flasks as a negligible amount of material is lost through
evaporation
 If the reaction involves gases, equilibrium can only be reached in a
closed system

Le Chatelier's Principle
Position of the equilibrium

 The position of the equilibrium refers to the relative amounts of

products and reactants in an equilibrium mixture.
 When the position of equilibrium shifts to the left, it means the
concentration of reactants increases
 When the position of equilibrium shifts to the right, it means the
concentration of products increases

Le Chatelier’s principle

 Le Chatelier’s principle says that if a change is made to a system at

dynamic equilibrium, the position of the equilibrium moves to minimise
this change
 The principle is used to predict changes to the position of equilibrium
when there are changes in temperature, pressure or concentration

Effects of concentration
Effects of pressure

 Changes in pressure only affect reactions where the reactants or products are gases

Effects of temperature

Effects of catalysts

 A catalyst is a substance that increases the rate of a chemical reaction

(they increase the rate of the forward and reverse reaction equally)
 Catalysts only cause a reaction to reach its equilibrium faster
 Catalysts therefore have no effect on the position of the
equilibrium once this is reached
Equilibrium expression & constant

 The equilibrium expression is an expression that links the equilibrium

constant, Kc, to the concentrations of reactants and products at
equilibrium taking the stoichiometry of the equation into account
 So, for a given reaction:

aA + bB ⇌ cC + dD

the Kc is defined as follows:

Equilibrium expression linking the equilibrium concentration of reactants

and products at equilibrium

 Solids are ignored in equilibrium expressions

 The Kc of a reaction is specific and only changes if the temperature of
the reaction changes
Partial pressure

 For reactions involving mixtures of gases, the equilibrium constant Kp is

used as it is easier to measure the pressure than the concentration for
gases
 The partial pressure of a gas is the pressure that the gas would have if
it was in the container all by itself
 The total pressure is the sum of the partial pressure

Mole fraction

 The mole fraction of a gas is the ratio of moles of a particular gas to the total number of moles
of gas present

Equation to calculate the mole fraction of a particular gas in a gas mixture

 To calculate the partial pressures of each gas the following relationship can be used:

Equation to calculate the partial pressure of a particular gas in a gas mixture

The sum of the mole fractions should add up to 1.00, while the sum of the partial pressures
should add up to the total pressure.
Equilibrium expressions involving partial pressures

 Equilibrium expressions in terms of partial pressures are written similarly to those involving
concentrations with a few differences:

Calculations involving Kc

 In the equilibrium expression each figure within a square bracket

represents the concentration in mol dm-3
 The units of Kc therefore depend on the form of the equilibrium
expression
 Some questions give the number of moles of each of the reactants and
products at equilibrium together with the volume of the reaction
mixture
 The concentrations of the reactants and products can then be calculated
from the number of moles and total volume
Calculating Kp of hydrogen iodide equilibrium reaction

 Step 1: Calculate the total number of moles

Total number of moles = 1.71 x 10-3 + 2.91 x 10-3 + 1.65 x 10-2

= 2.112 x 10-2

 Step 2: Calculate the mole fraction of each gas

 Step 3: Calculate the partial pressure of each gas

H2 = 0.0810 x 100 = 8.10 kPa

I2 = 0.1378 x 100 = 13.78 kPa

HI = 0.7813 x 100 = 78.13 kPa

  Step 4: Write the equilibrium constant in terms of partial pressure

 Step 5: Substitute the values into the equilibrium expression

= 54.7

 Step 6: Deduce the correct units for Kp

All units cancel out

Therefore, Kp = 54.7

 Other questions related to equilibrium expressions may involve

calculating quantities present at equilibrium given appropriate data

Changes that Affect the Equilibrium Constant

Changes in concentration

 If all other conditions stay the same, the equilibrium constant Kc is not
affected by any changes in concentration of the reactants or products
 For example, the decomposition of hydrogen iodide:

2HI ⇌ H2 + I2

The equilibrium expression is:

  Adding more HI makes the ratio of [ products ] to [ reactants ] smaller
 To restore equilibrium, [H2] and [I2] increases and [HI] decreases
 Equilibrium is restored when the ratio is 6.25 x 10-3 again
Changes in pressure

 A change in pressure only changes the position of the

equilibrium (see Le Chatelier’s principle)
 If all other conditions stay the same, the equilibrium constant Kc is not
affected by any changes in pressure of the reactants and products

Changes in temperature

 Changes in temperature change the equilibrium constant Kc

 For an endothermic reaction such as:

 An increase in temperature:
 [H2] and [I2] increases
 [HI] decreases

 Because [H2] and [I2] are increasing and [HI] is decreasing, the
equilibrium constant Kc increases

 For an exothermic reaction such as:

 An increase in temperature:
 [SO3] decreases
 [SO2] and [O2] increases
Because [SO3] decreases and [SO2] and [O2] increases the equilibrium
constant Kc decreases

Presence of a catalyst

 If all other conditions stay the same, the equilibrium constant Kc is not
affected by the presence of a catalyst
 A catalyst speeds up both the forward and reverse reactions at the same
rate so the ratio of [ products ] to [ reactants ] remains unchanged
  Equilibrium reactions are involved in some stages of large-scale production of certain
chemicals
 An understanding of equilibrium and Le Chatelier’s principle is therefore very important
in the chemical industry

Haber process

 The Haber process involves the synthesis of ammonia according to:

N2(g) + 3H2(g) ⇌ 2NH3(g) ΔHr = -92 kJ mol-1

 Le Chatelier’s principle is used to get the best yield of ammonia

Maximising the ammonia yield

Pressure

 An increase in pressure will result in the equilibrium shifting in the direction of the
fewest molecules of gas formed to reduce the pressure
 In this case, the equilibrium shifts towards the right so the yield of ammonia increases
 An increase in pressure will cause the particles to be closer together and therefore
increasing the number of successful collisions leading to an increased reaction rate
 Very high pressures are expensive to produce therefore a compromise pressure of 200
atm is chosen

Temperature

 To get the maximum yield of ammonia the position of equilibrium should be shifted as
far as possible to the right as possible
 Since the Haber process is an exothermic reaction, according to Le Chatelier’s principle
the equilibrium will shift to the right if the temperature is lowered
 A decrease in temperature will decrease the energy of the surroundings so the reaction
will go in the direction in which energy is released to counteract this
 Since the reaction is exothermic, the equilibrium shifts to the right
 However, at a low temperature the gases won’t have enough kinetic energy to collide
and react and therefore equilibrium would not be reached therefore compromise
temperature of 400-450 oC is used in the Haber process
 A heat exchanger warms the incoming gas mixture to give molecules more kinetic
energy such that the gas molecules collide more frequently increasing the likelihood of
a reaction

Removing ammonia
  Removing ammonia by condensing it to a liquid causes the equilibrium position to
shift to the right to replace the ammonia causing more ammonia to be formed from
hydrogen and nitrogen
 The removed ammonia is stored at very low temperatures and there is no
catalyst present with the stored ammonia so the decomposition reaction of ammonia to
decompose back into hydrogen and nitrogen will be too slow

Catalysts

 In the absence of a catalyst the reaction is so slow that hardly anything happens in a
reasonable time!
 Adding an iron catalyst speeds up the rate of reaction

Contact process

 The Contact process involves the synthesis of sulfuric acid according to:

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

 Le Chatelier’s principle is used to get the best yield of sulfuric acid

Maximising the sulfuric acid yield

Pressure

 An increase in pressure will result in the equilibrium shifting in the direction of the
fewest molecules of gas formed to reduce the pressure
 In this case, the equilibrium shifts towards the right so the yield of sulfuric acid increases
 In practice, the reaction is carried out at only 1 atm
 This is because Kp for this reaction is already very high meaning that the position of the
equilibrium is already far over to the right
 Higher pressures than 1 atm will be unnecessary and expensive

Temperature

 The same principle applies to increasing the temperature in the Contact process as in the
Haber process
 A compromise temperature of 450 oC is used

Removing sulfuric acid

 SO3 is removed by absorbing it in 98% sulfuric acid

 The SO3 reacts with the solution and more H2SO4 is formed
Catalysts

 The Contact process uses vanadium(V) oxide as a catalyst to increase the rate of reaction
 An acid is a substance that neutralises a base forming a salt and water:

2HCl(aq) + CaO(s) ⇌ CaCl2(aq) + H2O(l)

acid salt

 Acids are also substances that release hydrogen ions when they
dissolve in water:

 In organic acids (such as carboxylic acids) only some of the hydrogen atoms can form ions when
the acid dissociates

 A base is a compound that neutralises an acid forming a salt and water

2HCl(aq) + CaO(s) ⇌ CaCl2(aq) + H2O(l)

base salt

 A base is a substance that accepts hydrogen ions or a compound that

contains oxide or hydroxide ions

For example:

NH3(g) + H2O(l) → NH4+(aq) + OH-(aq)

base hydroxide ions

  A base that is soluble in water is called an alkali

Names & formulae of some common alkalis table

Brønsted–Lowry Theory
 The Brønsted-Lowry Theory defines acids and bases in terms of
proton transfer between chemical compounds
 A Brønsted-Lowry acid is a species that gives away a proton (H+)
 A Brønsted-Lowry base is a species that accepts a proton (H+) using
its lone pair of electrons
 Species that can act both as acids and bases are called amphoteric

 Eg. water as a Brønsted-Lowry acid

Strong acids

 A strong acid is an acid that dissociates almost completely in aqueous

solutions

 HCl (hydrochloric acid), HNO3 (nitric acid) and H2SO4 (sulfuric acid)

 The position of the equilibrium is so far over to the right that you can
represent the reaction as an irreversible reaction
 The position of the equilibrium is so far over to the right that you can
represent the reaction as an irreversible reaction
 Since the pH depends on the concentration of H+/H3O+ ions, the pH can
be calculated if the concentration of the strong acid is known

 A weak acid is an acid that partially (or incompletely) dissociates in

aqueous solutions
  Eg. most organic acids (ethanoic acid), HCN (hydrocyanic acid),
H2S (hydrogen sulfide) and H2CO3 (carbonic acid)

 The position of the equilibrium is more over to the left and an

equilibrium is established
 A weak acid is an acid that partially (or incompletely) dissociates in
aqueous solutions

 Eg. most organic acids (ethanoic acid), HCN (hydrocyanic acid),

H2S (hydrogen sulfide) and H2CO3 (carbonic acid)

 The position of the equilibrium is more over to the left and an

equilibrium is established

 The solution is less acidic due to the lower concentration of

H+/H3O+ ions
 Finding the pH of a weak acid is a bit more complicated as now the
concentration of H+ ions is not equal to the concentration of acid
 To find the concentration of H+ ions, the acid dissociation constant (Ka)
should be used
Acid & equilibrium position table

Strong bases

 A strong base is a base that dissociates almost completely in aqueous

solutions

E.g. group 1 metal hydroxides such as NaOH (sodium hydroxide)

The position of the equilibrium is so far over to the right that you can
represent the reaction as an irreversible reaction

 The solution formed is highly basic due to the high concentration of the
OH- ions

Weak bases

 A weak base is a base that partially (or incompletely) dissociates in

aqueous solutions
o NH3 (ammonia), amines and some hydroxides of transition metals
 The position of the equilibrium is more to the left and an equilibrium is
established
  The solution is less basic due to the lower concentration of OH- ions

Base & equilibrium position table

  The pH scale is a numerical scale that shows how acidic or alkaline a
solution is
 The values on the pH scale go from 1-14 (extremely acidic substances
have values of below 1)
 All acids have pH values of below 7, all alkalis have pH values above 7
 The lower the pH then the more acidic the solution is
 The higher the pH then the more alkaline the solution is

pH of acids

 Acidic solutions (strong or weak) always have more H+ than OH- ions
 Since the concentration of H+ is always greater than the concentration
of OH- ions, [H+] is always greater than 10-7 mol dm-3
 Using the pH formula, this means that the pH of acidic solutions is
always below 7
 The higher the [H+] of the acid, the lower the pH

pH of bases

 Basic solutions (strong or weak) always have more OH- than H+ ions
 Since the concentration of OH- is always greater than the concentration
of H+ ions, [H+] is always smaller than 10-7 mol dm-3
 Using the pH formula, this means that the pH of basic solutions is
always above 7
 The higher the [OH-] of the base, the higher the pH
pH Titration Curves
What are pH titration curves

 Titration is a technique used in neutralisation reactions between acids

and alkalis to determine the concentration of the unknown solution
 It involves adding a titrant of known concentration from a burette into
a conical flask containing the analyte of unknown concentration
 An indicator is added which will change colour at the endpoint of the
titration
 The endpoint is the point at which equal number of moles
of titrant and analyte react with each other
 The equivalence point is halfway the vertical region of the curve

Equivalence point → moles of alkali = moles of acid

 This is also known as the equivalence point and this is the point at
which neutralisation takes place

The diagram shows a pH titration curve where the equivalence point is

the point at which equal number of moles of titrant and analyte have
reacted
Sketching pH titration curve

 Draw axes with volume added (cm3) on the x-axis and pH on the y-axis

 Draw a horizontal line running parallel to the x-axis at pH 7

o Everything below this line will be in the acidic region and
everything above it in the alkaline region

 Determine which substance is in the conical flask

o If it is a strong acid the initial pH is about 1 or 2
o If it is a weak acid the initial pH is about 2-3
o If it is a strong alkali the initial pH is about 13-14
 o If it is a weak alkali the initial pH is about 11

 Determine what type of acids and alkali are used

o Strong acid + strong alkali
o Strong acid + weak alkali
o Weak acid + strong alkali
o Weak acid + weak alkali
  Draw the pH titration curve

Strong acid + strong alkali pH titration curve

 Initially there are only H+ ions present in solution from the dissociation
of the strong acid (HCl) (initial pH about 1-2)
 As the volume of strong alkali (NaOH) added increases, the pH of the
HCl solution slightly increases too as more and more H+ ions react with
the OH- from the NaOH to form water
 The change in pH is not that much until the volume added gets close to
the equivalence point
 The pH surges upwards very steeply
 The equivalence point is the point at which all H+ ions have been
neutralised (therefore pH is 7 at equivalence point)
 Adding more NaOH will increase the pH as now there is an excess in
OH- ions (final pH about 13-14)
 The diagram shows a pH titration curve of 1.0 mol dm-3 HCl (25 cm3)
with NaOH

 The pH titration curve for HCl added to a NaOH has the same shape
 The initial pH and final pH are the other way around
 The equivalence point is still 7
Reaction Kinetics
Reaction rate

 The rate of a reaction is the speed at which a chemical reaction takes

place and has units mol dm-3 s-1
 The rate of a reaction can be calculated by:

Step 1: Calculate the amount of ethyl ethanoate formed in mol

= 0.0005 mol

 Step 2: Calculate the volume of the reaction mixture in dm3

400 cm3 = 0.400 dm3

  Step 3: Calculate the concentration change of product formed

= 0.00125 mol dm-3

 Step 4: Calculate the time in seconds

1.0 min = 60.0 s

 Step 5: Use the equation to calculate the rate

= 2.08 x 10-5 mol dm-3 s-1

Collision theory

 The collision theory states that for a chemical reaction to take place the
particles need to collide with each other in the correct orientation and
with enough energy
 The minimum energy that colliding particles must have for a collision to
be successful and a reaction to take place is called the activation
energy (Ea)
Collision theory table

 An ineffective collision is when particles collide in the wrong

orientation or when they don’t have enough energy and bounce
off each other without causing a chemical reaction
Increase in reaction rate

 The collision frequency is the number of collisions per unit time

 When more collision per unit time take place, the number of particles
with energy greater than the Ea increases
 This causes an increase in rate of reaction
 A catalyst is a substance that increases the rate of reaction without
taking part in the chemical reaction by providing the particles an
alternative mechanism with a lower activation energy

Rate of Reaction: Concentration & Pressure

Concentration

 The more concentrated a solution is, the greater the number of particles in a
given volume of solvent
 An increase in concentration causes in an increased collision frequency and
therefore an increased rate of reaction

The diagram shows a higher concentration of particles in (b) which means that
there are more particles present in the same volume than (a) so the chances and
frequency of collisions between reacting particles is increased causing an increased
rate of reaction
Pressure

 An increase in pressure in reactions that involve gases has the same effect as
an increased concentration of solutions
 When the pressure is increased, the molecules have less space in which they
can move
 This means that the number of effective collisions increases due to an
increased collision frequency
 An increase in pressure therefore increases the rate of reaction

The diagram shows a higher pressure in (b) which means that the same number of
particles occupy a smaller volume, resulting in an increased collision frequency and
therefore increased rate of reaction

Rate of Reaction: Experimental Calculations

 During a reaction, the reactants are used up and changed into the products
 This means that as the reaction proceeds, the concentration of the reactants
is decreasing and the concentration of the products is increasing
 Because of this, the rate of the reaction is not the same throughout the
reaction but changes
 The rate of reaction during the reaction can be calculated from
a concentration-time graph.
Calculating the rate at the start of a reaction

 At the start of the reaction, the concentration-time curve looks almost

linear
 The rate at this point can therefore be found by treating the curve as a
linear line and by using:

 Using the graph, the average rate of the reaction over the first 5 minutes
for propene is:

Line a shows the average rate over the first five minutes whereas line b
shows the actual initial rate found by drawing a tangent at the start of
the curve. The calculated rates are very similar for both methods
 = 0.0009 mol dm-3 s-1

Calculating the rate as the reaction proceeds

 The curve becomes shallower with time which means that the rate
decreases with time
 The rate of reaction can be calculated by taking short time intervals

Eg. you can calculate the rate of reaction from 15 to 20 mins during
which the concentration of propene increases from 0.68 to 0.83 mol dm-
3
:

= 0.0005 mol dm-3 s-1

 The smaller the time intervals, the more accurate the reaction rate value
is
 Even more accurate is to find the rate of reaction at different
concentrations of reactant or product at particular time points
 This can be done by drawing tangents at several points on the graph
Activation Energy

 For a reaction to take place, the reactant particles need to overcome a

minimum amount of energy
 This energy is called the activation energy (Ea)
 In exothermic reactions the reactants are higher in energy than the
products
 In endothermic reactions the reactants are lower in energy than the
products
 Therefore, the Ea in endothermic reactions in endothermic reactions is
relatively larger than in exothermic reaction

The diagram shows that the reactants are higher in energy than the
products in the exothermic reaction, so the energy needed for the
reactants to go over the energy barrier is relatively small
 The diagram shows that the reactants are lower in energy than the
products in the endothermic reaction, so the energy needed for the
reactants to go over the energy barrier is relatively large

 Even though particles collide with each other in the same orientation, if
they don’t possess a minimum energy that corresponds to the Ea of that
reaction, the reaction will not take place
 Therefore, for a collision to be effective the reactant particles must
collide in the correct orientation AND possess a minimum energy equal
to the Ea of that reaction
Boltzmann distribution curve

 The Boltzmann distribution curve is a graph that shows the

distribution of energies at a certain temperature
 In a sample of a substance, a few particles will have very low energy, a
few particles will have very high energy, and many particles will have
energy in between

The Boltzmann distribution curve shows the distribution of the energies

and the activation energy

 The graph shows that only a small proportion of molecules in the

sample have enough energy for an effective collision and for
a chemical reaction to take place
Changes in temperature

 When the temperature of a reaction mixture is increased, the particles

gain more kinetic energy
 This causes the particles to move around faster resulting in
more frequent collisions
 Furthermore, the proportion of successful collisions increases, meaning
a higher proportion of the particles possess the minimum amount of
energy (activation energy) to cause a chemical reaction
 With higher temperatures, the Boltzmann distribution
curve flattens and the peak shifts to the right

The Boltzmann distribution curve at T oC and when the temperature is

increased by 10 oC
 Therefore, an increase in temperature causes an increased rate of
reaction due to:

 There being more effective collisions as the particles have more

kinetic energy, making them move around faster
 A greater proportion of the molecules having kinetic
energy greater than the activation energy

 Catalyst provide the reactants another pathway which has a lower

activation energy
 By lowering Ea, a greater proportion of molecules in the reaction
mixture have sufficient energy for an effective collision
 As a result of this, the rate of the catalysed reaction is increased
compared to the uncatalyzed reaction
Catalysts
 Catalysis is the process in which the rate of a chemical reaction is
increased, by adding a substance called a catalyst
 A catalyst increases the rate of a reaction by providing the reactants
with an alternative reaction pathway which is lower in activation
energy than the uncatalysed reaction
 Catalysts can be divided into two types:
o Homogeneous catalysts
o Heterogeneous catalysts
 Homogeneous means that the catalyst is in the same phase as the
reactants
o For example, the reactants and the catalysts are all liquids
 Heterogeneous means that the catalyst is in a different phase to the
reactants
o For example, the reactants are gases but the catalyst used is a
solid