Chem Factsheet

September 2000 N umber 01

Atomic Structure
The particles within a nucleus are drawn together by extremely powerful
To succeed in this topic you need to:
forces capable of overcoming the repulsion of the protons (+ve to +ve)
• be able to use the periodic table to find atomic and mass numbers.
However, these forces act over a short distance as they do not pull the
electrons in.
After working through this Factsheet you will be able to:
• describe and understand the accepted model of an atom
• interpret simple mass spectra The electrons are in constant motion, orbiting the nucleus.
• understand the importance of ionisation energies of different elements,
and use them as evidence in describing atomic structure Atomic number, atomic mass number and isotopes
• assign electronic configurations to atoms
• understand the impact of electronic configuration on chemical Atomic number (Z): the number of protons in an atom
properties Mass number (A): the number of protons + neutrons in an atom.
• define electron affinity

Exam Hint: A thorough understanding of atomic structure is

essential for success throughout AS Chemistry. Questions often
require candidates to
Remember also that the number of protons (+ve charges) will be equal to
• work out the electronic configuration of an atom the number of electrons (-ve charges) in a neutral atom.
• deduce chemical properties from electronic configuration
• describe and explain trends in ionisation energy Given the information on the periodic table, it is possible to calculate the
• interpret mass spectra number of protons, neutrons and electrons present in an atom of any given
element. Fig 2.
Fundamental particles
An atom is the smallest particle of a chemical element. Atoms themselves Fig 2.
consist of protons, neutrons (in the nucleus) and electrons (see Fig 1). The
mass of an atom is concentrated in the nucleus. The nucleus is very small mass number
9
and massive, so therefore has an incredibly high density.

Fig 1. Fundamental particles of an atom

4
Be
atomic number

Atomic number = 4 ∴ number of protons = 4

No. protons = no. electrons ∴ number of electrons = 4
electrons Mass number = no. p + no. n ∴ number of neutrons = 9 – 4 = 5

All atoms of the same element have the same atomic number - e.g atomic
number of magnesium = 12, therefore all magnesium atoms contain 12
protons.

nucleus Mass numbers of atoms of the same element may, however, vary – due to
(contains protons different atoms containing different numbers of neutrons. These atoms are
and neutrons called isotopes.

Remember - Isotopes of one particular element are atoms which

have the same atomic number and so the same number of protons
(therefore are atoms of the same element) but different mass numbers,
Table 1 Shows the relative charge, relative mass and position of atomic
because they have different numbers of neutrons.
particles. (For most purposes, the mass of the electron is taken as 0).

Table 1. Atomic particles data One example is hydrogen - there are three isotopes, all with atomic number
Particle Relative mass Relative charge Position within 1, but with mass numbers 1, 2 and 3.
atom
Proton 1 +1 Elements with isotopes do pose a problem when wanting to assign a mass
nucleus number on for the element. An average atomic mass is calculated - called
Neutron 1 0 nucleus the relative atomic mass, Ar. The calculation of this average mass needs
to take account of the relative abundance of each isotope; the method for
Electron 1 -1 shells doing this is illustrated in the following example:
1850

1
Atomic Structure Chem Factsheet

For example, naturally occuring chlorine consists of 2 isotopes. Ionisation Energies

75% of the atoms have a mass of 35 (Cl-35) If an atom is supplied with enough energy, it will lose an electron, and
25% of the atoms have a mass of 37 (Cl-37) additional supplies of energy may cause the loss of a second electron, then
75 25
a third and so on. If a neutral atom loses an electron, it becomes a positively
To work out Ar, we do × 35 + × 37 = 35.5 charged ion (cation).
100 100

The actual definition of relative atomic mass involves carbon - 12 - this

must be learnt. First Ionisation Energy - the energy required to remove 1 mole of
electrons from 1 mole of gaseous atoms.
mass of one atom of an element e.g. Na(g) → Na+(g) + e- ΔHIE = +494 KJ mol-1
Relative Atomic Mass (Ar) =
1/12 mass of one atom of carbon–12
Second Ionisation Energy - the energy required to remove 1 mole of
electrons from 1 mole of gaseous 1+ charged cations
e.g. Na+(g) → Na2+(g) + e- ΔHIE2 = +4564 KJ mol-1
Carbon – 12 is used to because carbon is a common element and as a solid
is easy to store and transport.
Examining successive ionisation energies for an element can give us further insight
into atomic structure – specifically the arrangement of electrons (Fig 6 overleaf)).

The mass spectrometer

The mass spectometer is a machine which provides chemists with a way
Fig 4. Mass spectrometer traces
to measure and compare masses of atoms and molecules (Fig 3.)
Sodium
(100 %)
Fig 3. Mass Spectrometer 100 sodium (Na)
80
% abundace

+
60
1. 3. 40
20
4.
0
0 10 20 30 40 70 80
2. Mass / Charge Ratio
1. vaporisation Iron
To
2. ionisation vacuum pump 100
3. accleration
(91.68%)
(by electric field)
4. deflection
5.
5
Relative Abundance / %

(by magnetic field)

5. detection

50
The way in which the mass spectrometer works can be broken down into
5 stages.
1. Vaporisation - The sample being tested has to be turned into a gas,
so individual atoms/molecules are separated. (2.17%)

2. Ionisation - A heated filament gives out electrons into the ionisation (5.84%) (0.31%)
0
chamber. As the sample enters the ionisation chamber, its atoms/ 20 30 40 50 60 70 80
molecules are bombarded by these electrons. The collisions cause Mass / Charge Ratio
electrons to be removed from the atoms/molecules of the sample, so
positive ions are formed. (This is where fragmentation can occur –
molecules may break into pieces.) From the mass spectra shown, it is clear that the sodium sample tested
consisted solely of sodium –23.
3. Acceleration - An electric field is applied, which will accelerate the
positive ions (as they are charges particles). The sample of iron was a mixture of 4 isotopes, iron –54, iron –56,
iron –57 and iron –58. The percentage abundancies are given (i.e. 91.68%
4. Deflections - A magnetic field deflects the beam of ions. Ions with iron –56, showing it to be the most common isotope) so now the relative
a high mass/charge ratio (eg. Heavy, 1+ charge) will be deflected less atomic mass of iron can be calculated.
than ions with a low mass/charge (e.g. light 13+ charge)
Ar = avge mass = 5.84 × 54 + 91.68 × 56 + 2.17 × 57 + 0.31 × 58= 55.91
100 100 100 100
5. Detection - Those ions which have the correct mass/charge ratio will
be detected. If the magnetic field is kept constant whilst the electric
field causing acceleration is continuously varied, one species after Note:many ions have a charge of +1, so the mass/charge (m/e) ratio is
another will be detected, so a complete spectrum, or trace, is obtained. equal to the mass (m) of the ion.

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Atomic Structure Chem Factsheet

Fig 5. Successive ionisation energies for sodium Notice that within a period, sets of elements with similar first ionisation
energies exist, consisting o f 2, 3, 3, members - within period 2, this is (Li, Be)
1000000 these 2 electrons are in the n=1 shell, (B,C,N) and (O, F, Ne). These are explained by the existence of subshells
closest to the nucleus. These - see later.
experience very strong attractive
100000 forces from the nucleus.
There is also a trend in first IEs down any group – there is a general
decrease due to the increased distance and shielding of the outer electrons
ionisation energy / kJ mol-1

10000 from the nucleus.

these 8 electrons are in the n=2 shell,
1000 between the n=1 and n=3 shells. Electronic Configurations
These electrons experience strong
attractive forces from the nucleus
You are aware that electrons exist in different energy levels (or quantum
100
shells).
this electron is in the n=3 shell,
furthest from the nucleus. This Electrons can also be split within a quantum shell, into subshells.
10 electron experiences comparatively
weak attractive forces from the
nucleus. e.g. in the second shell (referred to as" n = 2") there are 8 electrons in a full
0 shell. This can be split into 2 subshells:
0 1 2 3 4 5 6 7 8 9 10 11 • 2s - containing 2 electrons slightly harder to remove
ionisation number • 2p -containing 6 electrons slightly easier to remove.

The pattern shows us that sodium has 11 electrons arranged in 3 shells, or Each sub-shell is a collection of orbitals:
energy levels. The first electron is relatively easy to remove as:
(a) it exists further from the nucleus Sub-shell orbitals max e-
(b) the electrons orbiting closer to the nucleus ‘shield’ it from the positive s 1 2
centre so the attractive forces are comparatively weak. p 3 6
The next 8 electrons have similar ionisation energies (as they are all a d 5 10
similar distance from the nucleus) but do get successively slightly harder to f 7 14
remove, as the relative positive charge in the ion is increasing. The last 2
electrons are very difficult to remove as they exist very close to an Fig 7 shows the orbitals for the s and p sub-shells
unshielded nucleus.
Fig 7. s and p orbitals
Ionisation Energy and the Periodic Table
• alkali metals are the easiest to ionize three p-orbitals
• noble gases are the hardest to ionize s-orbital p-orbital
• As we move across a period, the first IE tends to increase, as
♦ nuclear charge increases
♦ electrons are added to the same shell, the same distance from the
nucleus with the same degree of shielding
Fig 6. First ionisation energies for the first 20 elements

Each orbital can hold up to 2 electrons, but electrons in a pair must have
opposing spin. We represent each orbital by a box, and the electrons by
Each 'peak' marks a noble gas (He, half-arrows. One half arrow points up and one down, to represent the
Ne, Ar) at the end of each period different spins of the two electrons

He
Ne
first ionistaion energy

F Ar When electron sub shells are filling up, one electron is placed in each
N available orbital first; the electrons only pair up when no more orbitals are
Cl
H C O P
Be available in that sub-shell.
Mg S
B Si Ca
Li Na Al
K

0 10 20
atomic number
Each 'trough' marks an alkali Exam Hint:
metal (Li,Na, K) at the start • You need to be able to draw the shapes of the s and p orbitals,
of each period but not of d or f orbitals.
• You need to know the number of orbitals - and hence number of
electrons - in each sub-
shell.

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Atomic Structure Chem Factsheet

Order of filling of sub-shells Table 2. Electronic arrangement of the elements from hydrogen
We already know that the electrons in an atom fill up the first shell before to krypton
going into the second, and fill that before going into the third shell. We now Element Atomic 1s 2s 2p 3s 3p 3d 4s 4p
need to look at the order in which the sub-shells fill up. This is described number
by Fig 9.
Hydrogen 1 1
Fig 9. Order of filling of sub-shells Helium 2 2
!s level full

1s Lithium 3 2 1
Beryllium 4 2 2
2s 2p 2s level full
3s 3p 3d
Boron 5 2 2 1
4s 4p 4d 4f Carbon 6 2 2 2
Nitrogen 7 2 2 3
5s 5p 5d 5f Oxygen 8 2 2 4
Fluorine 9 2 2 5
6s 6p 6d
Neon 10 2 2 6
2p level full

Using the diagram, the order in which the subshells fill is: Sodium 11 2 2 6 1
Magnesium 12 2 2 6 2
3s level full
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p .... etc
Aluminium 13 2 2 6 2 1
Silicon 14 2 2 6 2 2
We are now able to write out electronic configurations in more detail, using Phosphorus 15 2 2 6 2 3
the following notation: Sulphur 16 2 2 6 2 4
Chlorine 17 2 2 6 2 5

2p
number of electrons
5 in subshell Argon 18 2 2 6 2 6
3p level full
shell
number subshell Potassium 19 2 2 6 2 6 1
Calcium 20 2 2 6 2 6 2
or using arrows in boxes 4s level full
2p
Scandium 21 2 2 6 2 6 1 2
Titanium 22 2 2 6 2 6 2 2
Vanadium 23 2 2 6 2 6 3 2
Using the principles covered so far, we can now find the electronic Chromium 24 2 2 6 2 6 5 1 **
configurations of the first 36 elements (Table2) Manganese 25 2 2 6 2 6 5 2
Iron 26 2 2 6 2 6 6 2
Evidence for sub-shells from ionisation energies Cobalt 27 2 2 6 2 6 7 2
Whilst there is a general increase in IE across the period, this is not a Nickel 28 2 2 6 2 6 8 2
smooth trend, which can be explained by the existence of sub-shells. Copper 29 2 2 6 2 6 10 1 **
Zinc 30 2 2 6 2 6 10 2
3d level full
Fig 10. First ionisation energies across period 2
Gallium 31 2 2 6 2 6 10 2 1
Germanium 32 2 2 6 2 6 10 2 2
Arsenic 33 2 2 6 2 6 10 2 3
Ne Selenium 34 2 2 6 2 6 10 2 4
filling of 2p Bromine 35 2 2 6 2 6 10 2 5
sub-shell Krypton 36 2 2 6 2 6 10 2 6
F
first ionisation energy

4p level full
N pairing of
2p electrons N ote: a) how the 4s level fills up before the 3d level,
filling of 2s C
Be O b) for chromium and copper (labelled **) the sequence is out of
sub-shell step; you will meet this point again when studying the
2p sub-shell half-fills transition elements.
B You will be required to write the electronic arrangement (or configuration)
Li for elements and there are two accepted ways for doing this. For example,
the electronic arrangement for iron could be written: 1s2, 2s2, 2p6, 3s2, 3p6,
atomic number 3d6, 4s2 or [Ar] 3d6, 4s2 where [Ar] represents the electronic arrangement
of the noble gas argon.

4
Atomic Structure Chem Factsheet

You will notice from Fig 10 that the first ionisation energy decreases from Both F and Cl need to gain 1 electron to acquire a stable noble gas electronic
Be to B and from N to O. A similar phenomenon occurs between groups 2 configuration. An electron would be more strongly attracted to F rather
to 3 and 5 to 6 in the other periods. This can be explained by examining the than the larger Cl, as it could join a lower energy level closer to the nucleus
electron configurations of the elements: with less shielding from it. Therefore, the smaller the halogen atom, the
more reactive it is. So reactivity decreases down the group.
Comparing Be and B
Electron Affinities
1s 2s 2p 1s 2s 2p
As shown with the halogens, it is possible to add electrons to an atom,
Be B
forming a negative ion (anion). The energy required to do this is the electron
affinity.
Beryllium has full-subshell stability, as the highest occupied subshell is
complete. Boron has one electron in a higher (2p) sub-shell, which is easier
to remove, hence its 1st IE is lower than that of Be
First Electron Affinity - the energy required to add1 mole of electrons
Comparing N and O to 1 mole of gaseous atoms.
e.g. O (g) + e- → O− (g) ΔHEA1 = -141 kJ mol-
1s 2s 2p 1s 2s 2p
N O Second Electron Affinity - the energy required to add 1 mole of electrons
to 1 mole of gaseous 1- charged anions
Nitrogen has half-shell stability. e.g. O− (g) + e- → O2− (g) ΔHEA2 = +798 kJ mol-1

Oxygen has one 2p orbital which has a pair of electrons and paired electrons
repel, so one of these electrons is easier to remove, hence it has a lower 1st The 1st EA is always exothermic (energy is released) because the electron
IE than that of nitrogen. goes into a vacancy in the outer energy level. This is ‘bond-making’ so
energy is released.
Electronic Structure and Chemical Properties
Chemical reactions involve the making and/or breaking of bonds. Bond However, this creates a 1- ion so to put the second electron into the vacant
involve the movement of electrons. site needs energy to be put in to overcome the repulsion (–ve to –ve)
between the ion and the electron - so the 2nd EA is always endothermic
e.g. Covalent bond - sharing of electrons (energy is absorbed).
Ionic bond - transfer of electrons
Questions
It makes sense therefore that the electronic configuration of an atom has an 1. a) Define the terms first ionisation energy.
impact on its chemical properties.
b) The graph shows a plot of lg (ionisation energy) vs number of the
Any group on the periodic table can be considered a ‘family of elements’ as electron removed for aluminium.
the elements in that group will exhibit similar chemical properties. This is
due to each member of the group having the same number of electrons
in its outer shell.

Even within groups, trends in reactivity can be explained by electronic

configuration:
lg(ionisation energy)

e.g.1 For Group 1 – the alkali metals – reactivity increases down

the group.

If we consider lithium and sodium, their electron configurations are as

follows:
Li: 1s2 2s1
Na: 1s2 2s2 2p6 3s1

Both Li and Na require to lose 1 electron to gain a stable noble gas electronic 0 1 2 3 4 5 6 7 8 9 10 11 12 13
configuration. It is difficult to remove the outer electron from lithium as it number of electrons removed
is close to the nucleus and experiencing little shielding. These factors mean Explain the form of this graph in terms of the electron structure of
lithium: aluminium.
• has a higher 1st IE than sodium
• is less reactive than sodium 2. a) Define the terms
This trend continues down the group. (i) atomic number (ii) mass number
(iii) relative atomic mass (iv) isotope
e.g.2 For Group 7 – the halogens – reactivity decreases down the
group. b) Describe in detail the five stages in the operation of a mass
spectrometer.
If we consider fluorine and chlorine, their electron configurations are as
follows: c) The mass spectrometer analysis of neon shows it exists of two
F: 1s2 2s2 2p5 isotopes of different relative abundances ie. 20 (90%) and 22 (10%).
Cl: 1s2 2s2 2p6 3s2 3p5 Calculate the relative atomic mass of neon.

5
Atomic Structure Chem Factsheet

3. Sketch a graph on the axes below to show the successive ionisation 3.

energies of sodium.

lg (ionisation energy)
lg(ionisation energy)

0 1 2 3 4 5 6 7 8 9
0 1 2 3 4 5 6 7 8 9 10 11
number of electrons removed
number of electrons

Na is 2, 8 1. There is one electron in the outer orbit, 8 electrons in the

Give reasons for the shape of the line you draw. next orbit and 2 in the innermost orbit.

4. For each of the following elements give the electronic configuration 4. a) P = 15 1s2 2s2 2p6 3s2 3p3
in terms of s, p and d orbitals’: b) C = 6 1s2 2s2 2p2
a) phosphorus
b) carbon 5. a) 1st I.E’s decrease down a Group.
The outer electron is further from the nucleus and the inner electron
5. Explain the trend in first ionisation energies and the reasons for it: orbitals shield the pull of the nucleus on the outer electrons. The
a) down a group outer electrons are easier to remove.
b) across a period
b) 1st I.E’s increase across a Period.
The outer electrons go into the same outer orbital so the shielding
6. a) Why is the first ionisation energy of nitrogen higher than that of
effect is the same across the Period. At the same time one extra
oxygen?
proton is added, increased the nuclear charge. This makes the outer
electrons increasingly more difficult to remove.
b) Write equations which represent for oxygen:
6. a) N is 1s2 2s2 2p3 O is 1s2 2s2 2p4
(i) the first electron affinity Half-shell stability of p3, compared to O where the p electron
(ii) the second electron affinity is more easily removed.

7. Give reasons for each of the following: b) (i) O (g) + e- ‘ O- (g)

a) sodium is more reactive than magnesium (ii) O- (g) + e- ‘ O2- (g)
b) potassium is more reactive than sodium
c) chlorine is less reactive than fluorine 7. a) Na only has to lose one electron to gain the Noble Gas configuration,
and its 1st I.E. is lower than for magnesium. The Na single electron
Answers is lost more easily, so sodium is more reactive.
1. a) The energy needed to remove one mole of electrons from 1 mole of
b) K has a bigger atomic number so more electron orbits. Increased
gaseous atoms.
shielding on an electron further from the nucleus means the outer
b) Al has a 2, 8, 3 configuration ie. 3 outer electrons, 8 electrons in the
electron is easier to remove than the one for Na..
next orbialt and 2 electrons in the inner orbital.
c) F has a smaller atomic number so less electron orbits so less shielding
2. a) (i) number of protons in the nucleus
of the pull of the nucleus for the electron needed to complete is
(ii) number of protons and neutrons in the nucleus
outer orbital. The F atom therefore has more pull on electrons so is
(iii) the mass of an atom compared to 1/12 mass of an atom of
more reactive than Cl.
carbon 12
(iv) atoms with the same atomic number but different mass numbers/
atoms with the same number of protons but different numbers
of neutrons

b) Vaporisation – heating the sample to turn it into a gas

Ionisation – bombarding the gaseous sample with an electron beam
to remove electrons and produce positive ions.
Acceleration – attraction of the positive ions to an electrical field.
Acknowledgements:
Deflection – passing the ions through a magnetic field to deflect This Factsheet was researched and written by Sam Goodman
them according to mass/charge ratio. Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
Detection – ions being measured according to mass/charge ratio B18 6NF
and their relative abundance being calculated.
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