A LEVEL CHEMISTRY NOTES

1.1.1 Particles in the Atom & Atomic

Structure
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Structure of an Atom

 All matter is composed of atoms, which are the smallest parts of an element that can
take place in chemical reactions
 Atoms are mostly made up of empty space around a very small, dense nucleus that
contains protons and neutrons
 The nucleus has an overall positive charge
o The protons have a positive charge and the neutrons have a neutral charge
 Negatively charged electrons are found in orbitals in the empty space around the
nucleus

The basic structure of an atom (not to scale)

Subatomic Particles

 The protons, neutrons and electrons that an atom is made up of are

called subatomic particles
 These subatomic particles are so small that it is not possible to measure their masses
and charges using conventional units (such as grams or coulombs)
 Instead, their masses and charges are compared to each other, and so are
called ‘relative atomic masses’ and ‘relative atomic charges’
 These are not actual charges and masses but charges and masses of particles relative
to each other
o Protons and neutrons have a very similar mass, so each is assigned a relative
mass of 1
o Electrons are 1836 times smaller than a proton and neutron, and so their mass
is often described as being negligible
 The relative mass and charge of the subatomic particles are:

Relative mass & charge of subatomic particles table

Exam Tip

You can see from the table how the relative mass of an electron is almost
negligibleThe charge of a single electron is -1.602 x 10-19 coulombs, whereas the charge of
a proton is +1.602 x 10-19 coulombs. So, relative to each other, their charges are -1 and +1
respectively

Atoms: Key Terms

 The atomic number (or proton number) is the number of protons in the nucleus of
an atom and has the symbol Z
o The atomic number is also equal to the number of electrons present in
a neutral atom of an element
o E.g. the atomic number of lithium is 3, meaning that a neutral lithium atom
has 3 protons and therefore, also has 3 electrons
 The mass number (or nucleon number) is the total number
of protons + neutrons in the nucleus of an atom, and has the symbol A
 The number of neutrons can be calculated by:
 Number of neutrons = mass number - atomic number


o Protons and neutrons are also called nucleons, because they are found in the
nucleus

Exam Tip

The mass (nucleon) and atomic (proton) number are given for each element in the
Periodic Table

1.1.2 Mass, Charge & Subatomic Particles

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Mass & Charge Distribution

 The mass of an atom is concentrated in the nucleus, because the nucleus contains the
heaviest subatomic particles (the neutrons and protons)
o The mass of the electron is negligible
 The nucleus is also positively charged due to the protons
 Electrons orbit the nucleus of the atom, contributing very little to its overall mass, but
creating a ‘cloud’ of negative charge
  The electrostatic attraction between the positive nucleus and negatively charged
electrons orbiting around it is what holds an atom together

The mass of the atom is concentrated in the positively charged nucleus which is attracted
to the negatively charged electrons orbiting around it

Behaviour of Subatomic Particles in an Electric Field

 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
o This proves that the electrons are negatively charged; like charges repel each
other
o 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
o This proves that the proton is positively charged
o 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
o Which proves that the particle is neutral in character; it is not attracted to, or
repelled by, the negative or positive plate
 The lighter electrons undergo much more deflection than the proton

1.1.3 Determining Subatomic Structure

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Determining the Subatomic Structure of Atoms & Ions

 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
 The number of subatomic particles in atoms and ions can be determined given their
atomic (proton) number, mass (nucleon) number and charge

Protons

 The atomic number of an atom and ion determines which element it is

 Therefore, all atoms and ions of the same element have the same number of protons
(atomic number) in the nucleus
o E.g. lithium has an atomic number of 3 (three protons) whereas beryllium has
atomic number of 4 (4 protons)
 The number of protons equals the atomic (proton) number
 The number of protons of an unknown element can be calculated by using its mass
number and number of neutrons:

Mass number = number of protons + number of neutrons

Number of protons = mass number - number of neutrons

Worked example: Determine the number of protons

Answer

 Answer 1: The atomic number of a magnesium atom is 12 suggesting that the number
of protons in the magnesium element is 12
o Therefore the number of protons in a Mg2+ ion is also 12
 Answer 2: The atomic number of a carbon atom is 6 suggesting that a carbon
atom has 6 protons in its nucleus
 Answer 3: Use the formula to calculate the number of protons

Number of protons = mass number - number of neutrons

Number of protons = 63 - 34

Number of protons = 29


o Element X is therefore copper

Electrons

 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
o A positively charged ion has lost electrons and therefore has fewer electrons
than protons
o A negatively charged ion has gained electrons and therefore
has more electrons than protons

Worked example: Determine the number of electrons

Answer
  Answer 1: The atomic number of a magnesium atom is 12 suggesting that the number
of protons in the neutral magnesium atom is 12
o However, the 2+ charge in Mg2+ ion suggests it has lost two electrons
o It only has 10 electrons left now
 Answer 2: The atomic number of a carbon atom is 6 suggesting that
the neutral carbon atom has 6 electrons orbiting around the nucleus
 Answer 3: The number of protons of element X can be calculated by:

Number of protons = mass number - number of neutrons

Number of protons = 63 - 34

Number of protons = 29


o The neutral atom of element X therefore also has 29 electrons

Neutrons

 The mass and atomic numbers can be used to find the number
of neutrons in ions and atoms:

Number of neutrons = mass number (A) - number of protons (Z)

Worked example: Determine the number of neutrons

Answer

 Answer 1: The atomic number of a magnesium atom is 12 and its mass number is 24

Number of neutrons = mass number (A) - number of protons (Z)

Number of neutrons = 24 - 12

Number of neutrons = 12


o The Mg2+ ion has 12 neutrons in its nucleus
 Answer 2: The atomic number of a carbon atom is 6 and its mass number is 12

Number of neutrons = mass number (A) - number of protons (Z)

 Number of neutrons = 12 - 6

Number of neutrons = 6


o The carbon atom has 6 neutrons in its nucleus
 Answer 3: The atomic number of an element X atom is 29 and its mass number is 63

Number of neutrons = mass number (A) - number of protons (Z)

Number of neutrons = 63 - 29

Number of neutrons = 34


o The neutral atom of element X has 34 neutrons in its nucleus

1.1.4 Atomic & Ionic Radius

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Atomic & Ionic Radius

Atomic radius

 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
The atomic radius of a hydrogen atom is determined by halving the distance between the
nuclei of two hydrogen atoms covalently bonded

 Atomic radii show predictable patterns across the Periodic Table

o They generally decrease across each Period
o They generally increase down each Group
 These trends can be explained by the electron shell theory
o Atomic radii decrease as you move across a Period as the atomic number
increases (increased positive nuclear charge) but at the same time extra
electrons are added to the same principal quantum shell
o The larger the nuclear charge, the greater the pull of the nuclei on the electrons
which results in smaller atoms
o Atomic radii increase moving down a Group as there is an increased number
of shells going down the Group
o The electrons in the inner shells repel the electrons in the outermost
shells, shielding them from the positive nuclear charge
o This weakens the pull of the nuclei on the electrons resulting in larger atoms
 Trends in the atomic radii across a period and down a group

 The diagram shows that the atomic radius increases sharply between the noble gas at
the end of each period and the alkali metal at the beginning of the next period
 This is because the alkali metals at the beginning of the next period have one extra
principal quantum shell
o This increases shielding of the outermost electrons and therefore increases the
atomic radius

Ionic radius

 The ionic radius of an element is a measure of the size of an ion

 Ionic radii show predictable patterns
o Ionic radii increase with increasing negative charge
o Ionic radii decrease with increasing positive charge
 These trends can also be explained by the electron shell theory
o Ions with negative charges are formed by atoms accepting extra electrons
while the nuclear charge remains the same
o The outermost electrons are further away from the positively charged nucleus
and are therefore held only weakly to the nucleus which increases the ionic
radius
o The greater the negative charge, the larger the ionic radius
o Positively charged ions are formed by atoms losing electrons
o The nuclear charge remains the same but there are now fewer electrons
which undergo a greater electrostatic force of attraction to the nucleus
which decreases the ionic radius
o The greater the positive charger, the smaller the ionic radius
 Trends in the ionic radii across a period and down a group

1.1.5 Isotopes
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Isotopes: Basics

 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
o Eg. carbon-12 and carbon-14 are isotopes of carbon containing 6 and 8
neutrons respectively
 The atomic structure and symbols of the three isotopes of hydrogen

Isotopes: Chemical & Physical Properties

 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.

1.1.6 Electronic Structure

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Electron Shells: Basics

Shells

 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
  Principal quantum numbers (n) are used to number the energy levels or
quantum shells
o The lower the principal quantum number, the closer the shell is to the
nucleus
o The higher the principal quantum number, the higher the energy of the
shell
 Each principal quantum number has a fixed number of electrons it can hold
o n = 1 : up to 2 electrons
o n = 2 : up to 8 electrons
o n = 3 : up to 18 electrons
o n = 4 : up to 32 electrons

Electrons are arranged in principal quantum shells, which are numbered by

principal quantum numbers

Subshells

 The principal quantum shells are split into subshells which are given the
letters s, p and d
o Elements with more than 57 electrons also have an f shell
o 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
as seen in the diagram below:
 Electrons are arranged in principal quantum shells, which are numbered by
principal quantum numbers

Orbitals

 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
o 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:
o s : one orbital (1 x 2 = total of 2 electrons)
o p : three orbitals ( 3 x 2 = total of 6 electrons)
o d : five orbitals (5 x 2 = total of 10 electrons)
o f : seven orbitals (7 x 2 = total of 14 electrons)
 The orbitals have specific 3-D shapes
 Representation of orbitals (the dot represents the nucleus of the atom) showing
spherical s orbitals (a), p orbitals containing ‘lobes’ along the x, y and z axis

 Note that the shape of the d orbitals is not required at AS Level

An overview of the shells, subshells and orbitals in an atom

Ground state

 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

The ground state of an atom is achieved by filling the lowest energy subshells
first

1.1.7 Electron Subshells & Orbitals

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Electron Orbitals

 Each shell can be divided further into subshells, labelled s, p, d and f

 Each subshell can hold a specific number of orbitals:
o s subshell : 1 orbital
o p subshell : 3 orbitals labelled px, py and pz
o d subshell : 5 orbitals
o f subshell : 7 orbitals
 Each orbital can hold a maximum number of 2 electrons so the maximum number of
electrons in each subshell are as follows:
o s : 1 x 2 = total of 2 electrons
o p : 3 x 2 = total of 6 electrons
o d : 5 x 2 = total of 10 electrons
o f : 7 x 2 = total of 14 electrons
 In the ground state, orbitals in the same subshell have the same energy and are said to
be degenerate, so the energy of a px orbital is the same as a py orbital
 Shells are divided into subshells which are further divided into orbitals

Summary of the arrangement of electrons in atoms table

Subshells & Energy

 The principal quantum shells increase in energy with increasing principal

quantum number
o E.g. n = 4 is higher in energy than n = 2
 The subshells increase in energy as follows: s ＜ p ＜ d ＜ f
o The only exception to these rules is the 3d orbital which has slightly higher
energy than the 4s orbital
o Because of this, the 4s orbital is filled before the 3d orbital
 All the orbitals in the same subshell have the same energy and are said to
be degenerate
o E.g. px, py and pz are all equal in energy
 Relative energies of the shells and subshells

The s & p Orbitals

s orbitals

 The s orbitals are spherical in shape

 The size of the s orbitals increases with increasing shell number
o E.g. the s orbital of the third quantum shell (n = 3) is bigger than the s orbital
of the first quantum shell (n = 1)

The s orbitals become larger with increasing principal quantum number

p orbitals

 The p orbitals are dumbbell-shaped

 Every shell has three p orbitals except for the first one (n = 1)
 The p orbitals occupy the x, y and z-axis and point at right angles to each other so are
oriented perpendicular to one another
 The lobes of the p orbitals become larger and longer with increasing shell number

The p orbitals become larger and longer with increasing principal quantum number.

1.1.8 Electron Configuration

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Electron Configurations: Basics

 The electron configuration gives information about the number of electrons in

each shell, subshell and orbital of an atom
 The subshells are filled in order of increasing energy

The electron configuration shows the number of electrons occupying a subshell in a

specific shell

Electron Configurations: Explained

 Electrons can be imagined as small spinning charges which rotate around their own
axis in either a clockwise or anticlockwise direction
o The spin of the electron is represented by its direction
 Electrons can spin either in a clockwise or anticlockwise direction around their own axis

 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
o Eg. if there are three electrons in a p subshell, one electron will go into each
px, py and pz orbital

Electron configuration: three electrons in a p subshell

 Electrons are only paired when there are no more empty orbitals available within a
subshell in which case the spins are the opposite spins to minimize repulsion
o Eg. if there are four electrons in a p subshell, one p orbital contains 2 electrons
with opposite spin and two orbitals contain one electron only

Electron configuration: four electrons in a p subshell

 The principal quantum number indicates the energy level of a particular shell but also
indicates the energy of the electrons in that shell
o A 2p electron is in the second shell and therefore has an energy corresponding
to n = 2
 Even though there is repulsion between negatively charged electrons (inter-electrons
repulsion), they occupy the same region of space in orbitals
  This is because the energy required to jump to successive empty orbital
is greater than the inter-electron repulsion
 For this reason, they pair up and occupy the lower energy levels first

Electron Box Notation

 The electron configuration can also be represented using the electrons in

boxes notation
 Each box represents an atomic orbital
 The boxes are arranged in order of increasing energy from lowest to highest
 The electrons are represented by opposite arrows to show the spin of the electrons
o Eg. the box notation for titanium is shown below
o Note that since the 3d subshell cannot be either full or half full, the second 4s
electron is not promoted to the 3d level and stays in the 4s orbital

The electrons in Titanium are arranged in their orbitals as shown. Electrons occupy the
lowest energy levels first before filling those with higher energy

Free Radicals

 A free radical is a species with one or more unpaired electron

 The unpaired electron in the free radical is shown as a dot
o Eg. a chlorine free radical has the electron configuration 1s22s22p63s23p5
o Two of the three p orbitals have paired electrons whereas one of them has an
unpaired electron.

One of the p orbitals has unpaired electrons in a chlorine radical

Exam Tip
Free radicals are formed when a molecule undergoes homolytic fission where the two
electrons of a covalent bond are split evenly between the two atoms.
1.1.9 Determining Electronic Configurations
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Determining Electronic Configurations

 Writing out the electronic configuration tells us how the electrons in an atom or ion
are arranged in their shells, subshells and orbitals
 This can be done using the full electron configuration or the shorthand version
o The full electron configuration describes the arrangement of all electrons from
the 1s subshell up
o The shorthand electron configuration includes using the symbol of the nearest
preceding noble gas to account for however many electrons are in that noble
gas
 Ions are formed when atoms lose or gain electrons
o Negative ions are formed by adding electrons to the outer subshell
o Positive ions are formed by removing electrons from the outer subshell
o The transition metals fill the 4s subshell before the 3d subshell
but lose electrons from the 4s first and not from the 3d subshell (the 4s
subshell is lower in energy)
 The Periodic Table is split up into four main blocks depending on their electronic
configuration:
o s block elements
 Have their valence electron(s) in an s orbital
o p block elements
 Have their valence electron(s) in a p orbital
o d block elements
 Have their valence electron(s) in a d orbital
o f block elements
 Have their valence electron(s) in an f orbital

The elements can be divided into four blocks according to their outer shell electron
configuration

Exceptions

 Chromium and copper have the following electron configurations, which are different
to what you may expect:
 o Cr is [Ar] 3d5 4s1 not [Ar] 3d4 4s2
o Cu is [Ar] 3d10 4s1 not [Ar] 3d9 4s2
 This is because the [Ar] 3d5 4s1 and [Ar] 3d10 4s1 configurations are energetically
stable

Worked example: Electron configuration

Answer

Answer 1: Potassium has 19 electrons so the full electronic configuration is:

1s2 2s2 2p6 3s2 3p6 4s1

The 4s orbital is lower in energy than the 3d subshell and is therefore filled first

The nearest preceding noble gas to potassium is argon which accounts for 18 electrons so
the shorthand electron configuration is:

[Ar] 4s1

Answer 2: Calcium has 20 electrons so the full electronic configuration is:

1s2 2s2 2p6 3s2 3p6 4s2

The 4s orbital is lower in energy than the 3d subshell and is therefore filled first

The shorthand version is [Ar] 4s2 since argon is the nearest preceding noble gas to calcium
which accounts for 18 electrons

Answer 3: Gallium has 31 electrons so the full electronic configuration is:

[Ar] 3d10 4s2 4p1

Answer 4: What this means is that if you ionise calcium and remove two of its outer
electrons, the electronic configuration of the Ca2+ ion is identical to that of argon

Ca2+ is 1s2 2s2 2p6 3s2 3p6

Ar is also 1s2 2s2 2p6 3s2 3p6

1.1.10 Ionisation Energy
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Ionisation Energies

 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 units of IE are kilojoules per mole (kJ mol-1)
 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
o E.g. the first ionisation energy of gaseous calcium:

Ca(g) → Ca+ (g) + e- IE1 = +590 kJ mol-1

Trends in Ionisation Energies

 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:
o Size of the nuclear charge
o Distance of outer electrons from the nucleus
o Shielding effect of inner electrons
o Spin-pair repulsion
 First ionisation energy increases across a period and decreases down a group

A graph showing the ionisation energies of the elements hydrogen to sodium

Ionisation energy across a period

 The ionisation energy across a period generally increases due to the following
factors:
o Across a period the nuclear charge increases
o 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
o The shielding by inner shell electrons remain reasonably constant as electrons
are being added to the same shell
o It becomes harder to remove an electron as you move across a period; more
energy is needed
o So, the ionisation energy increases

Dips in the trend

 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
o Beryllium has a first ionisation energy of 900 kJ mol-1 as its electron
configuration is 1s2 2s2
o Boron has a first ionisation energy of 800 kJ mol-1 as its electron
configuration is 1s2 2s2 2px1
 There is a slight decrease in IE1 between nitrogen and oxygen due to spin-pair
repulsion in the 2px orbital of oxygen
o Nitrogen has a first ionisation energy of 1400 kJ mol-1 as its electron
configuration is 1s2 2s2 2px1 2py1 2pz1
o Oxygen has a first ionisation energy of 1310 kJ mol-1 as its electron
configuration is 1s2 2s2 2px2 2py1 2pz1
o In oxygen, there are 2 electrons in the 2px orbital, so the repulsion between
those electrons makes it slightly easier for one of those electrons to be
removed

From one period to the next

 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:
o There is increased distance between the nucleus and the outer electrons as you
have added a new shell
o There is increased shielding by inner electrons because of the added shell
o These two factors outweigh the increased nuclear charge

Ionisation energy down a group

 The ionisation energy down a group decreases due to the following factors:
o The number of protons in the atom is increased, so the nuclear
charge increases
 o But, the atomic radius of the atoms increases as you are adding more shells of
electrons, making the atoms bigger
o So, the distance between the nucleus and outer electron increases as you
descend the group
o The shielding by inner shell electrons increases as there are more shells of
electrons
o These factors outweigh the increased nuclear charge, meaning it
becomes easier to remove the outer electron as you descend a group
o So, the ionisation energy decreases

Ionisation Energy Trends across a Period & going down a Group Table

1.1.12 Ionisation Energies & Electronic

Configurations
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Ionisation Energies: Explained

 Energy is required to remove an outer shell electron as this involves breaking

the attractive forces between the electron and the positively charged nucleus
 There are several factors which affect the magnitude of the ionisation energy:
 Nuclear charge
o Positive nuclear charge increases with increasing number of protons
o The greater the positive charge, the greater the attractive forces between the
outer electron(s) and the nucleus
o More energy is required to overcome these forces so ionisation
energy increases with increasing nuclear charge
 Shielding
o Electrons repel each other and electrons occupying the inner shells repel
electrons located in shells further outside the nucleus and prevent them from
feeling the full effect of the nuclear charge
o The greater the shielding effect is, the weaker the attractive forces between the
positive nucleus and the negatively charged electrons
o Less energy is required to overcome the weakened attractive forces so
ionisation energy decreases with increasing shielding effects

Shielding makes it easier to remove the outermost electrons

 Atomic/ionic radius
o The larger the radius, the greater the distance between the nucleus and the
outer shell electron(s)
o Increasing distance weakens the strength of the attractive forces
o Larger atoms/ions also result in greater shielding due to the presence of more
inner electrons
o Less energy is required to remove the outer shell electron(s) so ionisation
energy decreases with increasing atomic/ionic radius
 Spin-pair repulsion
o Spin pair repulsion occurs when the electron being removed is spin paired
with another electron in the same orbital
o The proximity of the like charges of electrons in the orbital results in repulsion
o Less energy is required to remove one of the electrons so ionisation
energy decreases when there is spin-pair repulsion
 Summary of factors affecting ionisation energies of atoms

Ionisation Energies: Electronic Configuration

 Successive ionisation data can be used to:

o Predict or confirm the simple electronic configuration of elements
o Confirm the number of electrons in the outer shell of an element
o Deduce the Group an element belongs to in the Periodic Table
 By analyzing where the large jumps appear and the number of electrons removed
when these large jumps occur, the electron configuration of an atom can be
determined
 Na, Mg and Al will be used as examples to deduce the electronic configuration and
positions of elements in the Periodic Table using their successive ionisation energies

Successive ionisation energies table

Sodium

 For sodium, there is a huge jump from the first to the second ionisation energy,
indicating that it is much easier to remove the first electron than the second
 Therefore, the first electron to be removed must be the last electron in
the valence shell thus Na belongs to group I
 The large jump corresponds to moving from the 3s to the full 2p subshell

Na 1s2 2s2 2p6 3s1

Magnesium

 There is a huge increase from the second to the third ionisation energy, indicating
that it is far easier to remove the first two electrons than the third
 Therefore the valence shell must contain only two electrons indicating that
magnesium belongs to group II
 The large jump corresponds to moving from the 3s to the full 2p subshell

Mg 1s2 2s2 2p6 3s2

Aluminium

 There is a huge increase from the third to the fourth ionisation energy, indicating
that it is far easier to remove the first three electrons than the fourth
 The 3p electron and 3s electrons are relatively easy to remove compared with the 2p
electrons which are located closer to the nucleus and experience
greater nuclear charge
 This is due to weakened shielding effects through the loss of three electrons
 The large jump corresponds to moving from the third shell to the second shell

Al 1s2 2s2 2p6 3s2 3p1

Exam Tip
Find the large jumps by subtracting the successive ionisation energies from each other to
identify when an electron has been removed from a different subshell.

1.2.1 Relative Masses

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Relative Masses
Atomic Mass Unit

 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

Relative atomic mass, Ar

 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

Relative isotopic mass

 The relative isotopic mass is the mass of a particular atom of an isotope compared to
the value of the unified atomic mass unit
 Atoms of the same element with a different number of neutrons are called isotopes
 Isotopes are represented by writing the mass number as 20Ne, or neon-20 or Ne-20
 o To calculate the average atomic mass of an element the percentage
abundance is taken into account
o Multiply the atomic mass by the percentage abundance for each isotope and
add them all together
o Divide by 100 to get average relative atomic mass
o This is known as the weighted average of the masses of the isotopes

Relative molecular mass, Mr

 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 Mr has no units

 The Mr can be found by adding up the relative atomic masses of all atoms present in
one molecule
 When calculating the Mr the simplest formula for the compound is used, also known
as the formula unit
o Eg. silicon dioxide has a giant covalent structure, however the simplest
formula (the formula unit) is SiO2

Relative formula mass, Mr

 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
 In the table above, the Mr for potassium carbonate, calcium hydroxide and ammonium
sulphates are relative formula masses.
Exam Tip
Remember: compound ions are ions that contain more than one type of element, such as OH-

1 1.2.2 The Mole & Avogadro Constant

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Mole & Avogadro Constant

 The Avogadro constant (NA or L) is the number of particles equivalent to the

relative atomic mass or molecular mass of a substance
o The Avogadro constant applies to atoms, molecules, ions and electrons
 The value of NA is 6.02 x 1023 g mol-1
 The mass of a substance with this number of particles is called a mole (mol)
o The mass of a substance containing the same number of fundamental units as
there are atoms in exactly 12.00 g of 12C
 One mole of any element is equal to the relative atomic mass of that element in grams
o 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
o One mole of water would have a mass of (2 x 1 + 16) = 18 g

Worked Example: Moles

Answer 1

The relative atomic mass of Na is 22.99

Therefore, 1 mol of Na has a mass of 22.99 g mol-1

1 mol of Na will contain 6.02 x 1023 atoms of Na (Avogadro’s constant)

Answer 2

The relative atomic mass of H is 1.005

Since there are 2 H atoms in H2, the mass of 1 mol of H2 is (2 x 1.005) 2.01 g mol-1

1 mol of H2 will contain 6.02 x 1023 molecules of H2

Since there are 2 H atoms in H2, 1 mol of H2 will contain 1.204 x 1024 H atoms
Answer 3

The relative atomic mass of Na and Cl is 22.99 and 35.45 respectively

Therefore, 1 mol of NaCl has a mass of (22.99 + 35.45) 58.44 g mol-1

1 mol of NaCl will contain 6.02 x 1023 molecules of NaCl

Since there are Na and Cl atoms in NaCl, 1 mol of NaCl will contain 1.204 x 1024 atoms in
total

. PHYSICAL CHEMISTRY

1.2.3 Formulae
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Formulae of Ionic Compounds

 Ionic compounds are formed from a metal and a nonmetal bonded together
 Ionic compounds are electrically neutral; the positive charges equal the negative
charges

Charges on positive ions

 All metals form positive ions

o There are some non-metal positive ions such as ammonium, NH4+, and
hydrogen, H+
 The metals in Group 1, Group 2 and Group 13 have a charge of 1+ and 2+ and 3+
respectively
 The charge on the ions of the transition elements can vary which is why Roman
numerals are often used to indicate their charge
 Roman numerals are used in some compounds formed from transition elements to
show the charge (or oxidation state) of metal ions
o Eg. in copper (II) oxide, the copper ion has a charge of 2+ whereas in copper
(III) nitrate, the copper has a charge of 3+
Non-metal ions

 The non-metals in group 15 to 17 have a negative charge and have the suffix ‘ide’
o Eg. nitride, chloride, bromide, iodide
 Elements in group 17 gain 1 electron so have a 1- charge, eg. Br-
 Elements in group 16 gain 2 electrons so have a 2- charge, eg. O2-
 Elements in group 15 gain 3 electrons so have a 3- charge, eg. N3-
 There are also more complex negative ions, which are negative ions made up of more
than one type of atom

The charges of simple ions depend on their position in the Periodic Table

Formulae of ionic compounds table

Worked Example: Formulae

Answer

Answer 1: Magnesium chloride

 Magnesium is in Group 2 so has a charge of 2+

 Chlorine is in group 17 so has a charge of 1-
 Magnesium needs two chlorine atoms for each magnesium atom to be balanced so the
formula is MgCl2

Answer 2: Iron (III) oxide

 The Roman numeral states that iron has a charge of 3+

 Oxygen is in group 16 so has a charge of 2-
 The charges need to be equal so 2 iron to 3 oxygen atoms will balance electrically, so
the formula is Fe2O3

Answer 3: Aluminum nitrate

 Aluminium is in group 13 so has a charge of 3+

 Nitrate is a compound ion and has a charge of 1-
 The complex ion needs to be placed in a bracket if more than 1 is needed
 The formula of aluminium nitrate is Al(NO3)3

1.2.4 Balancing Equations

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Balancing Equations

 A symbol equation is a shorthand way of describing a chemical reaction

using chemical symbols to show the number and type of each atom in the
reactants and products
 A word equation is a longer way of describing a chemical reaction using
only words to show the reactants and products

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
o E.g. the reaction needs to be balanced
  When balancing equations remember:
o Not to change any of the formulae
o To put the numbers used to balance the equation in front of the formulae
o To balance firstly the carbon, then the hydrogen and finally the oxygen
in combustion reactions of organic compounds
 When balancing equations follow the following the steps:
o Write the formulae of the reactants and products
o Count the numbers of atoms in each reactant and product
o Balance the atoms one at a time until all the atoms are balanced
o Use appropriate state symbols in the equation
 The physical state of reactants and products in a chemical reaction is specified
by using state symbols
o (s) solid
o (l) liquid
o (g) gas
o (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

Answer:

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)

Answer 1:

Step 1: To balance the equation, write out the symbol equation showing reactants and
products

Zn + CuSO4 → ZnSO4 + Cu

Step 2: Count the numbers of atoms in each reactant and product. The equation is
already balanced

Step 3: Use appropriate state symbols in the equation

Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)

Answer 2:

Step 1: The full chemical equation for the reaction is

Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)

Step 2: Break down reactants into their respective ions

Zn (s) + Cu2+ SO42- (aq) → Zn2+SO42- (aq) + Cu (s)

Step 3: Cancel the spectator ions on both sides to give the ionic equation
 Zn (s) + Cu2+SO42- (aq) → Zn2+SO42- (aq) + Cu (s)

Zn (s) + Cu2+(aq) → Zn2+ (aq) + Cu (s)

1.2.5 Empirical & Molecular Formulae

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Empirical & Molecular Formulae

 The molecular formula is the formula that shows the number and type of each atom
in a molecule
o 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
o Eg. the empirical formula of ethanoic acid is CH2O

 Organic molecules often have different empirical and molecular formulae

 Simple inorganic molecules however have often similar empirical and molecular
formulae
 Ionic compounds always have similar empirical and molecular formulae

Empirical & Molecular Formulae Calculations

Empirical formula

 Empirical formula is the simplest whole number ratio of the elements present in
one molecule or formula unit of the compound
 It is calculated from knowledge of the ratio of masses of each element in the
compound
 The empirical formula can be found by determining the mass of each element present
in a sample of the compound
 It can also be deduced from data that give the percentage compositions by mass of
the elements in a compound

Worked Example: Empirical formula from mass.

Answer

 Step 1: Calculate relative formula mass of empirical formula

Relative formula mass = (C x 4) + (H x 10) + (S x 1)

Relative formula mass = (12 x 4) + (1 x 10) + (32 x 1)

Relative formula mass = 90

 Step 2: Divide relative formula mass of X by relative formula mass of empirical

formula

Ratio between Mr of X and the Mr of the empirical formula = 180/90

Ratio between Mr of X and the Mr of the empirical formula = 2

 Step 3: Multiply each number of elements by 2

(C4 x 2) + (H10 x 2) + (S1 x 2) = (C8) + (H20) + (S2)

Molecular Formula of X is C8H20S2

1.2.6 Water of Crystallisation

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Water of Crystallisation

 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
 The water of crystallisation is separated from the main formula by a dot when writing
the chemical formula of hydrated compounds
o Eg. hydrated copper(II) sulfate is CuSO4∙5H2O
 A compound which doesn’t contain water of crystallisation is called an anhydrous
compound
o Eg. anhydrous copper(II) sulfate is CuSO4
 A compound can be hydrated to different degrees
o Eg. cobalt(II) chloride can be hydrated by six or two water molecules
o CoCl2 ∙6H2O or CoCl2 ∙2H2O
 The conversion of anhydrous compounds to hydrated compounds is reversible by
heating the hydrated salt

Anhydrous to hydrated salt:

CuSO4 + 5H2O → CuSO4∙5H2O

Hydrated to anhydrous salt (by heating):
CuSO4∙5H2O → CuSO4 + 5H2O
Exam Tip
To calculate the Mr of hydrated salts, the Mr of the salt and water should be
calculated separately and then added together.

1.2.7 Reacting Masses & Volumes

Mole Calculations

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

equation:

 It is important to be clear about the type of particle you are referring to when
dealing with moles
o Eg. 1 mole of CaF2 contains one mole of CaF2 formula units, but one mole
of Ca2+ and two moles of F- ions

Reacting masses

 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:
o The mass of the reactants
o The molar mass of the reactants
o The balanced equation

Percentage yield

 In a lot of reactions, not all reactants react to form products which can be due to
several factors:
o Other reactions take place simultaneously
o The reaction does not go to completion
o 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:
  Where actual yield is the number of moles or mass of product
obtained experimentally
 The predicted yield is the number of moles or mass obtained by calculation

Worked example: Mass calculation using moles

Answer

 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

Worked Example: Calculate % yield using moles

Answer

 Step 1: The symbol equation is:

Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)

 Step 2: Calculate the amount of zinc reacted in moles

 Step 3: Calculate the maximum amount of copper that could be formed from the
molar ratio:

Since the ratio of Zn(s) to Cu(s) is 1:1 a maximum of 0.10 moles can be produced

 Step 4: Calculate the maximum mass of copper that could be formed

(theoretical yield)

Mass = mol x Mr

Mass = 0.10 mol x 64 g mol-1

Mass = 6.4 g

 Step 5: Calculate the percentage yield of copper

Excess & limiting reagents

 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:
o The number of moles of the reactants should be calculated
o The ratio of the reactants shown in the equation should be taken into
account eg:

C + 2H2 → CH4
 There are 10 mol of Carbon reacting with 3 mol of Hydrogen

 Hydrogen is the limiting reagent and since the ratio of C : H2 is 1:2 only 1.5 mol
of C will react with 3 mol of H2

Worked example: Excess & limiting reagent

Answer

 Step 1: Calculate the moles of each reactant

 Step 2: Write the balanced equation and determine the molar ratio

2Na + S → Na2S

The molar ratio of Na: Na2S is 2:1

 Step 3: Compare the moles and determine the limiting reagent

So to react completely 0.40 moles of Na require 0.20 moles of S and since there are
0.25 moles of S, then S is in excess. Na is therefore the limiting reactant.

Volumes of gases

 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 dm 3
 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:

Worked example: Calculation volume of gas using excess & limiting
reagents

Answer

Volumes & concentrations of solutions

 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:
o Change mass in grams to moles
o Change cm3 to dm3
 To calculate the mass of a substance present in solution of
known concentration and volume:
o Rearrange the concentration equation

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


o Multiply the moles of solute by its molar mass

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

Worked example: Calculating volume from concentration

Answer

 Step 1: Write the balanced symbol equation

CaCO3 + 2HCl → CaCl2 + H2O + CO2

 Step 2: Calculate the amount, in moles, of calcium carbonate that reacts

 Step 3: Calculate the moles of hydrochloric acid required using the reaction’s
stoichiometry

1 mol of CaCO3 requires 2 mol of HCl

So 0.025 mol of CaCO3 requires 0.05 mol of HCl

 Step 4: Calculate the volume of HCl required

Volume of hydrochloric acid = 0.05 dm3

Worked example: Neutralisation calculation

Answer

 Step 1: Write the balanced symbol equation

Na2CO3 + 2HCl → Na2Cl2 + H2O + CO2

 Step 2: Calculate the amount, in moles, of sodium carbonate reacted by

rearranging the equation for amount of substance (mol) and dividing by the
volume by 1000 to convert cm3 to dm3

amount (Na2CO3) = 0.025 dm3 x 0.050 mol dm-3 = 0.00125 mol

 Step 3: Calculate the moles of hydrochloric acid required using the reaction’s
stoichiometry

1 mol of Na2CO3 reacts with 2 mol of HCl, so the molar ratio is 1 : 2

Therefore 0.00125 moles of Na2CO3 react with 0.00250 moles of HCl

 Step 4: Calculate the concentration, in mol dm-3 of hydrochloric acid

Concentration (HCl) (mol dm-3) = 0.125 mol dm-3

Stoichiometric relationships

 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:
  The gas volumes can be used to deduce the stoichiometry of a reaction
o Eg. in the combustion of 50 cm3 of propane reacting with 250 cm3 of
oxygen, 150 cm3 of carbon dioxide is formed suggesting that the ratio of
propane:oxygen:carbon dioxide is 1:5:3

C3H8 (g) + 5O2 (g) → 3CO2 (g) + H2O (l)

1. PHYSICAL CHEMISTRY

1. PHYSICAL CHEMISTRY

1. PHYSICAL CHEMISTRY

1. PHYSICAL CHEMISTRY1. PHYSICAL CHEMISTRY