Atomic Structure and thePeriodic

Table

1
 2. Atomic Structure and Periodic Table
Inside the Atom
Sub-atomic particles

1) Electrons revolve around in region of space called orbitals.

2) Electrons do not move in fixed orbits.
3) The nucleus is made up of protons and neutrons which contains almost allthe mass of the
atom. This is because the mass of electrons is very small compared to others.
4) The nucleus is positively-charged because of the protons. Electrons, beingnegatively-charged,
surround the nucleus.

Details of the three Sub-atomic (fundamental) Particles

Particle Position Relative Mass Relative Charge

Proton Nucleus 1 +1
Neutron Nucleus 1 0
Electron Orbitals 1/1840 -1

Behaviour of sub-atomic particles in electric field

1) Proton will be deflected towards the negativeplate

because it is positively-charged.

2) Electron will be deflected towards the positiveplate

because it is negatively-charged.

3) Neutron will not be deflected and continue in their direction of motion

because it is neutral(not charged).

4) Angle of deflection of electron > Angle of deflection of proton becausethe mass of

electron is smaller than proton. (angle of deflection is inversely proportional to charge/mass ratio)

2
5) Conclusion:
i. Protons are positively-charged
ii. Electrons are negatively-charged
iii. Neutrons are neutral
iv. Protons are much heavier than electron

Nucleon number and proton number

1) Proton number is the total number of protons in an atom.

2) Nucleon number is the total number of protons and neutrons in an atom.
3) Proton number is also known as atomic number while nucleon number is alsoknown as mass
number.
4) In a neutral atom, the total number of protons equals to the total number ofelectrons.

5) When an atom gains or loses electrons, a cation or anion will be formed.

6) Cation is a positively-charged ion. It is formed when an atom loses electron(s).In cation, the number
of protons is more than the number of electrons.
7) Anion is a negatively-charged ion. It is formed when an atom gains electron(s).In anion, the number
of electrons is more than the number of protons.
8) An atom or ion is said to be
i. isoelectronic if they have the same number of electrons.
ii. isotonic if they have the same number of neutrons.
iii. isotopic if they have the same number of protons.
To deduce the number of protons, neutrons and electrons in an atom/ion

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Isotopes

1) Isotopes are atoms of the same element with the same number of proton butdifferent
number of neutron.

Example:

2) Isotopes have the same:

i. number of protons and electrons
ii. electronic configuration
iii. chemical properties(because they have the same number of electrons)

3) Isotopes have different:

i. number of neutrons and nucleon number
ii. mass
iii. density
iv. molecular speed
4) Isotopes can be stable or unstable. Unstable isotopes are called radioactive
isotopes(radioisotopes).

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 The Mass Spectrometer

The mass spectrometer can be used to determine all the isotopes present in a sample of
an element and to therefore identify elements.

Ions are formed when an atom loses or gains electrons meaning it is no longer neutral
and will have an overall charge.

They are very useful in the analytical technique of mass spectrometry. It is used to
identify different isotopes and find the overall relative atomic mass of an element.

Time of Flight (TOF) Mass Spectrometry

This form of mass spectrometry records the time it takes for ions of each isotope to
reach a detector. Using this, spectra can be produced showing each isotope present.

1. Ionisation - A sample of an element is vapourised and injected into the mass

spectrometer where a high voltage is passed over the chamber. This causes
electrons to be removed from the atoms (they are ionised) leaving +1 charged ions
in the chamber.

2. Acceleration - These positively charged ions are then accelerated towards a

negatively charged detection plate.

3. Ion Drift - The ions are then deflected by a magnetic field into a curved path. The
radius of the path is dependent on the charge and mass of the ion.

4. Detection - When the positive ions hit the negatively charged detection plate, they
gain an electron, producing a flow of charge. The greater the current produced,
the greater the abundance of that particular ion.

5. Analysis - These current values are then used in combination with the flight times
to produce a spectra print-out with the relative abundance of each isotope
displayed.

During the ionisation process, a 2+ charged ion may be produced. This means it will be
affected more by the magnetic field producing a curved path of smaller radius. As a

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 result, its mass to charge ratio (m/z) is halved. This can be seen on spectra as a trace
at half the expected m/z value.

Calculating relative atomic mass

The relative atomic mass quoted on the periodic table is a weighted average of all the isotopes

Fig: spectra for

100 Magnesium from mass
spectrometer
80 78.70%
24Mg+ For each isotope the mass
% abundance

60 spectrometer can measure a m/z

40 (mass/charge ratio) and an abundance
25Mg+ 26Mg+

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

11.17% in a mass spectrum then give charge
and mass number e.g. 24Mg+
26 m/z
24 25

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 Sometimes two electrons may be
R.A.M =  (isotopic mass x % abundance) removed from a particle forming a 2+
ion. 24Mg2+ with a 2+ charge would
100 have a m/z of 12

For above example of Mg

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

Mass spectra for Cl2 and Br2

Cl has two isotopes Cl35 (75%) and Cl37(25%) Br has two isotopes Br79 (50%) and Br81(50%)

These lead to the following spectra caused by the diatomic molecules

Br79Br81 +
Br81Br79 +
Cl35Cl35 + relative
relative abundance
abundance Cl35Cl37 + Br79Br79 + Br81Br81 +
Cl37Cl37 +

70 72 74 m/z m/z
158 160 162

Measuring the Mr of a molecule Spectra for C4H10

If a molecule is put through a mass spectrometer it
will often break up and give a series of peaks caused Mass spectrum for butane
by the fragments. The peak with the largest m/z,
however, will be due to the complete molecule and 43
will be equal to the Mr of the molecule. This peak is Molecular ion
called the parent ion or molecular ion CH +
4 10

29

58

Uses of mass spectrometers

• Mass spectrometers have been included in planetary space probes so that elements on other
planets can be identified. Elements on other planets can have a different composition of
isotopes.
• Drug testing in sport to identify chemicals in the blood and to identify breakdown products from
drugs in body
• quality control in pharmaceutical industry and to identify molecules from sample with potential
biological activity
• radioactive dating to determine age of fossils or human remains

7
 Ionisation Energies
Definition : First ionisation energy Remember these
definitions very carefully
The first ionisation energy is the energy required when one mole of gaseous
atoms forms one mole of gaseous ions with a single positive charge
The equation for 1st ionisation
This is represented by the equation: H(g) → H+(g) + e- energy always follows the same
pattern.
It does not matter if the atom does
Always gaseous not normally form a +1 ion or is not
gaseous
Definition : Second ionisation energy
The second ionisation energy is the energy required when one mole of
gaseous ions with a single positive charge forms one mole of gaseous
ions with a double positive charge

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

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

Successive ionisation energies

The patterns in successive ionisation energies for an element give us important
information about the electronic structure for that element.

Why are successive ionisation energies always larger?

The second ionisation energy of an element is always bigger than the first ionisation energy.
When the first electron is removed a positive ion is formed.
The ion increases the attraction on the remaining electrons and so the energy required to
remove the next electron is larger.
How are ionisation energies linked to electronic structure?
Explanation
Ionisation The fifth electron is in a inner
energy shell closer to the nucleus and
therefore attracted much more
Notice the big strongly by the nucleus than the
jump between 4 fourth electron.
and 5. It also does not have any
shielding by inner complete shells
1 2 3 4 5 6 of electron
No of electrons removed

Example: What group must this element be in? Here there is a big jump between the 2nd and 3rd
ionisations energies which means that this
1 2 3 4 5 element must be in group 2 of the periodic table
Ionisation 590 1150 4940 6480 8120 as the 3rd electron is removed from an electron
energy kJ mol-1 shell closer to the nucleus with less shielding and
so has a larger ionisation energy

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The first Ionisation energy of the elements
The shape of the graph for periods two and
three is similar. A repeating pattern across a
Ionisation energy kJ mol-1

period is called periodicity.

2000

1500 The pattern in the first ionisation energy

gives us useful information about
1000 electronic structure
500
You need to carefully learn the
0 patterns
5 10 15 20
Atomic number

Q. Why has helium the largest first ionisation energy?

A. Its first electron is in the first shell closest to the nucleus and has no
shielding effects from inner shells. He has a bigger first ionisation Many questions can be
energy than H as it has one more proton answered by application of
the 3 factors that control
Q. Why do first ionisation energies decrease down a group? ionisation energy

A. As one goes down a group, the outer electrons are found in shells
further from the nucleus and are more shielded so the attraction of
the nucleus becomes smaller

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

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

the effective attraction of the nucleus greater. The electrons are being
added to the same shell which has the same shielding effect and the
electrons are pulled in closer to the nucleus.

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

This is because Na will have its outer electron in a 3s shell further from
the nucleus and is more shielded. So Na’s outer electron is easier to
remove and has a lower ionisation energy.

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

Al is starting to fill a 3p sub shell, whereas Mg has its outer electrons in the 3s
sub shell. The electrons in the 3p subshell are slightly easier to remove because
the 3p electrons are higher in energy and are also slightly shielded by the 3s
electrons
Learn carefully the
Q. Why is there a small drop from P to S? explanations for
these two small
With sulfur there are 4 electrons in the 3p sub shell and the 4th is starting to doubly fill drops as they are
the first 3p orbital. different to the
When the second electron is added to a 3p orbital there is a slight repulsion between usual factors
the two negatively charged electrons which makes the second electron easier to
remove.
3p 3p
3s 3s
Two electrons of opposite spin in
the same orbital
phosphorus 1s2 2s2 2p63s23p3
sulfur 1s2 2s2 2p63s23p4
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Patterns in the second ionisation energy.

If the graph of second ionisation or each successive element is plotted then a similar pattern to the first
ionisation energy is observed but all the elements will have shifted one to the left.
5000
Na
2nd Ionisation energy
4500
4000
(kJ/mol) 3500
3000 Ar
2500 S
P
2000 Al Cl
1500
Mg Si
1000
10 12 14 16 18 20
Atomic Number

The group 1 elements are now at the peaks of the graph

Lithium would now have the second largest ionisation of all elements as its second electron
would be removed from the first 1s shell closest to the nucleus and has no shielding effects
from inner shells. Li has a bigger second ionisation energy than He as it has more protons.

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Electronic Structure
Models of the atom
An early model of the atom was the Bohr model (GCSE model) (2 electrons in first shell, 8 in second etc.) with
electrons in spherical orbits. Early models of atomic structure predicted that atoms and ions with noble gas
electron arrangements should be stable.

The A-level model

Electrons are arranged on: Sub energy levels labelled s ,
p, d and f
Principle energy levels Split Orbitals which hold up
s holds up to 2 electrons Split
numbered 1,2,3,4.. into to 2 electrons of
p holds up to 6 electrons into
1 is closest to nucleus opposite spin
d holds up to 10 electrons
f holds up to 14 electrons

Shapes of orbitals
Orbitals represent the
Principle level 1 2 3 4 mathematical probabilities of
finding an electron at any point
within certain spatial
Sub-level distributions around the
1s 2s, 2p 3s, 3p, 3d 4s, 4p, 4d, 4f nucleus.
Each orbital has its own
approximate, three
An atom fills up the sub shells in order of increasing energy (note 3d is dimensional shape.
higher in energy than 4s and so gets filled after the 4s It is not possible to draw the
1s→2s→2p→3s→3p→ 4s→3d→4p→5s→4d→5p shape of orbitals precisely.

Writing electronic structure using letters and numbers • s sublevels are

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

Number of main Name of

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

The arrows going in the

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

When filling up sub levels with several

orbitals, fill each orbital singly before starting
to pair up the electrons

2p

Electronic structure for ions

When a positive ion is formed electrons are lost When a negative ion is formed electrons are gained
Mg is 1s2 2s2 2p6 3s2 but Mg2+ is 1s2 2s2 2p6 O is 1s2 2s2 2p4 but O2- is 1s2 2s2 2p6

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 Periodicity

Classification of elements in s, p, d blocks

Elements are classified as s, p or d block, according
to which orbitals the highest energy electrons are in.

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

Period 3 = Na, Mg, Al, Si, P, S, Cl, Ar

Atomic radius 0.18

0.16

atomic radius (nm)

Atomic radii decrease as you move from left to right
0.14
across a period, because the increased number of 0.12
protons create more positive charge attraction for 0.1
electrons which are in the same shell with similar 0.08
shielding. 0.06
0.04
0.02
Exactly the same trend in period 2 0
Na Mg Al Si P S Cl A
Along a period, atomic radius decreases. This is
due to an increased nuclear charge for the same
number of electron shells. The outer electrons are
pulled in closer to the nucleus as the increased
charge produces a greater attraction. As a result,
the atomic radius for that element is reduced.

Down a group, atomic radius increases. With

each increment down a group, an electron shell is
added each time. This increases the distance
between the outer electrons and the nucleus,
reducing the power of attraction. More shells
also increases electron shielding where the inner
shells create a ‘barrier’ that blocks the attractive
forces. Therefore, the nuclear attraction is
reduced further and atomic radius increase
Ionisation Energies

First ionisation energies follow a general increasing trend

along period 2. This is due to the decreasing atomic radius and
increasing nuclear charge so outer electrons are held more
strongly.

Boron and oxygen are exceptions to this trend due to the

quantum behaviour of the electrons.Between beryllium and
boron, electrons start to be added to a 2p orbital rather than
2s. The 2p orbital has a slightly higher energy level than the
2s orbital so this electron is found slightly further from the
nucleus. This means it can be removed more easily (less
energy required).
Between nitrogen and oxygen, electrons start to pair in the 2p
orbitals. The paired electrons areboth negatively charged so
they repel each other. This repulsion allows an electron to be
removed with less energy than expected.

Physical Properties of Period 3

Melting Points
The melting points of the period three elements is linked to the bond strength and structure:

Sodium, magnesium and aluminium are all metals with metallic bonding. Their melting points increase
due to greater positively charged ions (Na = +1, Mg = +2, Al = +3). This also meansmore electrons
are released as free electrons, so the attractive electrostatic forces increase from Na to Al.

Silicon is macromolecular meaning it has a very strong covalent structure. These covalentbonds
require a lot of energy to break giving it a very high melting point.

Phosphorus, sulphur and chlorine are all simple covalent molecules held with weak van derwaals
forces. These intermolecular forces don’t require much energy to overcome so these molecules have
relatively similar, low melting points.Argon is a noble gas that exists as individual atoms with a full
outer shell of electrons. Thismakes the atom very stable and the van der waals forces between
them very weak. As a result, the melting point of argon is very low and it exists as a gas at room
temperature.

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1st ionisation energy
The general trend across is to increase. This is due to

1st ionisation energy

1600
increasing number of protons as the electrons are being 1400
added to the same shell 1200

(kJ/mol)
1000
There is a small drop between Mg + Al. Mg has its outer 800
600
electrons in the 3s sub shell, whereas Al is starting to fill the
400
3p subshell. Al’s electron is slightly easier to remove
200
because the 3p electrons are higher in energy. 0
Na Mg Al Si P S Cl Ar
There is a small drop between phosphorous and sulfur.
Sulfur’s outer electron is paired up with an another electron in Exactly the same trend in period 2 with
the same 3p orbital. drops between Be & B and N to O for
When the second electron is added to an orbital there is a same reasons- make sure change 3s
slight repulsion between the two negatively charged and 3p to 2s and 2p in explanation!
electrons which makes the second electron easier to remove.

Melting and boiling points

For Na, Mg, Al- Metallic bonding : strong bonding – gets 3000
stronger the more electrons there are in the outer shell that are 2500

Melting and boiling

released to the sea of electrons. A smaller sized ion with a 2000

points (K)
greater positive charge also makes the bonding stronger. High
1500
energy is needed to break bonds.
1000
Si is Macromolecular: many strong covalent bonds between 500
atoms high energy needed to break covalent bonds– very high
0
mp +bp Na Mg Al Si P S Cl Ar
Cl2 (g), S8 (s), P4 (S)- simple Molecular : weak London forces
between molecules, so little energy is needed to break them – Similar trend in period 2
low mp+ bp Li,Be metallic bonding (high mp)
S8 has a higher mp than P4 because it has more electrons (S8 B,C macromolecular (very high mp)
=128)(P4=60) so has stronger London forces between N2,O2 molecular (gases! Low mp as
molecules small London Forces)
Ne monoatomic gas (very low mp)
Ar is monoatomic weak London Forces between atoms

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