Periodic Trends 1

Elements show trends in their physical and chemical properties across periods and
INORGANIC CHEMISTRY
down groups.

s block 18
p block
1 1 2 Group H 13 14 15 16 17 He
2 Li Be B C N O F Ne
d block
3 Na Mg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar
Period

4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

5 Rb Sr f block Y Zr Nb Mo Tc Ru Rh Pd Ag Cd n Sn Sb Te Xe

6 Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Os r Pt Au Hg TI Pb Bi Po At Rn

7 Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr Rf Db Sg Bh Hs Mt Ds Rg Cn 113 Fl 115 Lv 117 118

Figure 10.2 A modern form of the Periodic in rows or periods across the table. The elements in a period have different physical
The periodic table is divided into groups, periods and blocks. The International Union
Table. The elements shown in red are good and chemical properties, but trends become apparent in these properties as we move

1
conductors of electricity, and the ones shown
across a period.
of Pure and Applied Chemistry, IUPAC, now recommends that the groups in the
in blue are poor conductors. The pink shading
indicates that the principal form of the element
The s, p, d and f blocks
is a semiconductor. As only a few atoms of the
periodic table should be numbered 1 togroups
elements at the end of the Periodic Table have
The first two 18. form the s block (Groups 1 and 2). These have the outer
10_02 Cam/Chem AS&A2
been made, these have been left white. electronic configurations ns1 and ns2, respectively, where n is the number of the
•Barking
GroupsDog Art1 and 2 remain the same as before – classified as the s-block.
shell. The last six groups form the p block (Groups 13 to 18), in which the p
sub-shell is being progressively filled. These elements have the outer electronic
• The transition elements now become Group 3 to 12 – classified as the d-block.
configurations ns2 np1 to ns2 np6.
In between the s and p blocks is the d block (Groups 3–12), in which the d
• Groups 3 to 7 now become Groups 13 to 17 and the noble gases become Group
sub-shell is being progressively filled. Our study of the d block is largely restricted
to the elements scandium to zinc, and these elements have the outer electronic
18 – classified as the p-block. configurations 4s2 3d1 to 4s2 3d10, as we shall see in Topic 24.
About a quarter of the known elements belong to the f block. The first row, the
4f, includes all the elements from cerium (Ce) to lutetium (Lu) inclusive. In this block,
the f sub-shell in the fourth principal shell is being progressively filled. In the past,

All the elements in a group contain the same number of electrons in their outer shell.
these elements were called the ‘rare earths’. This was a misnomer, as their abundance
in the Earth’s crust is fairly large – for some it is comparable to that of lead. However,
For example, all the elements in group 1 have one electron in their outer shell, which is
it is true that they are mostly quite thinly spread, so mining them is quite expensive.
They are now called the lanthanoids, as their properties are similar to those of the
in an s-orbital. All the elements in group 17 have seven electrons in their outer orbit,
element lanthanum (La) that precedes them in the Periodic Table. Although they are
not particularly rare, the lanthanoids are difficult to purify from one another because
arranged s2p5. their chemical properties are nearly identical. The elements of the second row of the
f block, the 5f, are called the actinoids. All the actinoids are radioactive, and most
have to be made artificially.
The horizontal rows are called periods. All elements in the same period have the
same number of shells containing electrons. For example, all the
10.3 Periodic trends in the elements of elements in the third
period, Na to Ar, have electrons in the first, second and third
the third period (sodium to argon)shells.
1
In this section we shall look at the trends in the properties of the elements and their
18
Key
1 atomic number compounds in the third period of the Periodic Table. 2

H symbol He
1.0 2
relative atomic mass
Appearance 13 14 15 16 17 4.0
3 4 5 6 7 8 10 9
The elements on the left of the Periodic Table have low values of ionisation energy
Li Be B C N O F Ne
6.9 9.0
and electronegativity, and so they show the properties 10.8 12.0
associated
14.0
with
16.0
metallic
19.0 20.2
11 12 bonding (see section 4.11), for example, they13are shiny 14 and 15 conduct16 electricity.
17 In18
Na Mg the middle of the Periodic Table, elements with Al higherSi values P of ionisation
S ClenergyAr
24.3 3 4 5 6 7 8 9 11 12 27.0
23.0
and electronegativity are10semiconductors: they have 28.1 31.0
a dull shine to32.1 35.5
them and are 39.9
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
−12
K Ca Sc Ti V Cr poor
Mn conductors
Fe Co of electricity
Ni (typically
Cu Zn10 Ga times that
Ge of aAs metal).SeThe elements
Br Kr
39.1 40.1 45.0 47.9 50.9 52.0 on
54.9the right
55.8 of the
58.9 Periodic
58.7 Table,
63.5 with the highest
65.4 69.7 values
72.6 of74.9
ionisation
79.0 energy
79.9 and83.8
37 38 39 40 41 42 electronegativity,
43 44 45are dull46 in appearance
47 48 and are
49 such 50poor conductors
51 52 that53they are
54
Rb Sr Y Zr Nb Mo Tc as electrical
used Ru Rhinsulators
Pd (theirAg conductivities
Cd In are only
Sn about Sb 10−18 Tetimes Ithat ofXe
85.5 87.6 88.9 91.2 92.9 95.9 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 72 73 74 a 75
metal). 76 77 78 79 80 81 82 83 84 85 86
57-71
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
188
132.9 137.3 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0

87 88 89–103 104 105 106 107 108 109 110 111 112 114 116

Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Fl Lv

333_10_AS_Chem_BP_186-201.indd 188 18/09/14 1

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.9 140.1 140.9 144.2 144.9 150.4 152.0 157.2 158.9 162.5 164.9 167.3 168.9 173.0 175.0

89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 238.1

Figure 8.1 The periodic table.

The International Union of Pure and Applied Chemistry, IUPAC, now
recommends that the groups in the periodic table should be numbered
1 to 18.
● Groups 1 and 2 remain the same as before – classified as the s-block.
● The transition elements now become Group 3 to 12 – classified as
the d-block.
● Groups 3 to 7 now become Groups 13 to 17 and the noble gases
 ● Groups 3 to 7
Periodic Trends 2
now become Groups 13 to 17 and the noble gases
become Group 18 – classified as the p-block.
The table is also divided into blocks:
The blocks are shown in Figure 8.2.

s- p-
block block

d-
block

1
Figure 8.2 Blocks of the periodic table.
The s-block consists of the elements in groups 1 and 2. An s-block element has its
The vertical columns are called groups and the horizontal rows are
highest-energy electron in an s-orbital, i.e. the last electron added goes into an s-
called
orbital. periods. Trends in the groups (vertical columns) and periods
(horizontal rows) reflect the structures of the atoms of the elements
within
The them,in and
elements these in
the s-block areturn affect
reactive the These
metals. chemical
metalsproperties
(includingof the
potassium,
elements.
sodium, These
calcium andrepeating
magnesium)properties
are all highdemonstrate
in the activity periodicity.
(electrochemical) series.
They have lower densities, lower melting points and lower boiling points than most
other metals and they form stable, involatile ionic compounds.

Group 1: Also called the Alkali Metals. Soft, highly reactive group of metals. ns1. 30/03/15

Group 2. Also called the Alkaline Earth Metals. Fairly reactive metals. ns2

The d-block elements occupy space in the periodic table between Group 2 and
Group 13. The d-block contains the elements scandium to zinc in period 4 and
those elements below them.

A d-block element cannot be defined in terms of energy because the energy level of
the d-orbitals is altered by the presence of electrons in the outer s-orbital. It can only
be defined in aufbau terms, i.e. the last electron added to a d-block element goes into
a d-orbital.

These metals (including chromium, iron, copper, zinc and silver) are much less
reactive than the metals in Groups 1 and 2.
 Periodic Trends 3
Although the periodic table does not classify elements as metals and
The p-block contains
non-metals, there is athe elements
fairly in groups
obvious 13 tobetween
division 17 and group 18 (the
the two noble
(‘fairly obvious’,
but, notA ‘clear
gases). p-blockcut’). Separating
element the elements into
has its highest-energy either
electron in ametals or i.e.
p-orbital, non-metals
the last is
rather like trying to separate all
electron added goes into a p-orbital. the shades of grey into either black or white.
The fairly obvious division between metals and non-metals is shown by a thick
stepped line in Figure 9.5. The 20 or so non-metals are packed into
Some of the elements in the p-block are metals, like tin, lead and bismuth. They are the top
right-hand corner above the thick stepped line. Some of the elements next to
usually low in the activity (electrochemical) series and they have some resemblances

8
the thick steps, such as germanium, arsenic and antimony, have similarities to
to non-metals. Other elements in the p-block are non-mental.
both metals and non-metals and it is difficult to place these in one class or the

Group 17. Also called the Halogens. Very Periodicity

other. Chemists sometimes use the name metalloid for these elements which
reactive
are difficult to classify one way or the other. group of non-metals. ns 2 np5

8.1 The Periodic Table

Figure 9.8Also
Group 18. shows a classification
called of elements
the Noble Gases as metals,
because they metalloids
do not react. and non-
Form few

1
metals on the basis
compounds. ns np
2 6 of their electrical conductivity. In this classification:

Metalloids
Metals Non-metals
The Periodic Table is a list of all the elements in order of increasing atomic
number. You can predict the properties of an element from its position in
Li Be B C N O F Ne
the table. You can use it to explain the similarities of certain elements and
Na Mg Al Si P S Cl Ar
the trends in their properties, in terms of their electronic arrangements.
K Ca Ga Ge As Se Br Kr Non-metals
Metals
The structure
Rb Sr ofd-block
the andPeriodic Table
In Sn Sb Te I Xe
Cs Ba f-block metals Tl Pb Bi Po At Rn
The Periodic Table has been written in many forms including pyramids
and spirals.FrThe Ra one shown below is one common layout. Some areas
ofFigthe
9.8 Periodic Table
Classifying the are asgiven
elements metals,names.
metalloidsThese are shown
and non-metals in Figure
on the basis of their 1.
electrical conductivity. In this figure, metalloids are coloured grey
1 2 3 4 5 6 7 0
1 Metals are good conductors of electricity with atomic electrical conductivity*
1 greater than 10−3 ohm−1 cm−4.
noble (rare or inert) gases

2 Metalloids are poor conductors of electricity with atomic electrical conductivity

2 −3 −5 −1 −4
usually less than 10 but greater than 10 ohm cm .
alkaline earth metals

metalloids
3 3 Non-metals are virtually non-conductors (insulators). Their atomic electrical
halogens
alkali metals

−10 −1 −4
conductivity is usually less than 10 ohm cm .
4
Notice in Figure 9.8 that the cell for carbon is shaded less heavily than those for
5 transition metals
the other metalloids. This is because carbon exists as three different allotropes –
6 graphite, a poor conductor classed as a metalloid, plus diamond and fullerenes,
insulators classed as non-metals.
7
In spite of problems such as this, the classification of elements into metals,
metalloids and non-metals is useful and convenient.
Lanthanides
lanthanides

Actinides
actinides

▲ Figure 1 Named areas of the Periodic Table

Metals and non-metals

The red stepped line in Figure 1 (the ‘staircase line’) divides metals
(on its left) from non-metals (on its right). Elements that touch this
line, such as silicon, have a combination of metallic and non-metallic
properties. They are called metalloids or semi-metals. Silicon,
for example, is a non-metal but it looks quite shiny and conducts
electricity, although not as well as a metal.
 The Periodic Table reveals
period number. This so-called ‘short form’ of the periodic patterns
Metals, such as sodium, magnesium and aluminium, on the left of each periodin the properties
from Na table
→ Mg omits
of
→ Al. the t
e
Periodic Trends 4
with mobile, delocalised electrons in their structure are good conductors of
example, every time you go across a period you go from
electricity. When a battery is attached to them, electrons flow out of the metals
into the positive terminal of the battery. At the same time, electrons flow into
18 of pe
Group
left to non-metals
the metal on 13 the 14
from the negative terminal of the battery.
1 2 right. 15This is16 an example
17
On the other hand, metalloids and non-metals with molecular structures
Period
t word
have periodic
no mobile
almost nil.
1
electrons. means
This means recurring
that their electrical conductivity regularly.
is 2
1 H He
1 2
Periodicity
29.7
3 4 and 5
The properties
6
periodicity of7 of
atomic8 elements
9
properties 10 in
Li Be B C N O F Ne
Periodicity
2,1 is explained
2,2 2,3 by2,4the electron
2,5 2,6 arrangements
2,7 2,8 o
Table 9.3 shows the electronic (shell and sub-shell) structures for the elements In this section you will learn to:
in Periods 2 and 3.
11 12 13 14 15 16 17 18
• The 3 Na
elements Mg in Al
Groups Si 1,
Elements in the same group of the periodic table have similar electron 2, P and S
3 Cl
(sodium, Ar • Give the electronic structure
magne
of Period 2 and 3 elements
configurations. For2,8,1 2,8,2I elements
example, Group 2,8,3
(Li to Fr) 2,8,4 2,8,5
have one electron 2,8,6 2,8,7
and compare the number2,8,8
of
in their aluminium) 1
are
outer shells (ns ). Group II elements metals.
(Be to Ra) have twoThey have
electrons in giant structures.
electrons in the last sub-shell
19) and Group20VII elements (F to At) have seven outer shell

1
2 • Describe and explain changes in
their outer shells (ns
electronsouter
4 np ). As
(ns 2
K5
electrons Ca to
these electron configurationsform ionic
recur in a periodic compounds.
pattern,
it would not be surprising to find that atomic properties, such as atomic radii,
atomic and ionic radii as you go
across a period
2,8,8,1 energies,
ionic radii and ionisation 2,8,8,2show similar periodicity. • Describe and explain other
• Silicon
Atomic radii
in Group 4 has four electrons in its outer she
trends in atomic properties such
as first ionisation energies and
Based
The it
atomic on
forms
radii the
of electron
atoms four
can be arrangements
covalent
obtained from X-ray bonds.
analysis of
and the elements
The
electron (Chapter
element 12),
has the
some pe
electronegativity

divided intoof four blocks of elements (Figure

density maps. Using these techniques, it is possible to measure the distance
3.7):
between
properties and is classed as a semi-metal.
the nuclei atoms and then estimate the radius of individual atoms.

The periodicity
s-block
The atomic
■ elementsof
radii of metals are atomic
obtained properties
by measuring the distance between the KEY POINT

•thisisThe
radius simply half elements
of the ll inter-nuclear
look at the indistance.
Groups
nuclei of neighbouring atoms in metal crystals (Figure 9.10 (a)). The atomic
In section we trends 5, and
in atomic 6, and
ionic 7 (phosphorus, sulfu
Elements in the same group of the
radii, first ionisation
periodic energies
table have similar electron
■ p-block elements configurations. This results in
are non-metals.
and electronegativity as you goThey across aeither
period. accept electrons to form io
similar atomic properties.
■ d-block elements
or share their outer electrons to form covalent compou
Table 9.3 The electronic structures of the elements in Periods 2 and 3
Period 2
■ f-block
Electron shell structure
elements.
Li
2, 1 2, 2
Be B
2, 3
C
2, 4
N
2, 5
O
2, 6
F
2, 7
Ne
2, 8
• Argon in Group 0 is a noble gas – it has a full outer s
Electron sub-shell structure 1s22s1 1s22s2 1s22s22p1 1s22s22p2 1s22s22p3 1s22s22p4 1s22s22p5 1s22s22p6
Period 3 Na Mg Al Si P S Cl Ar
unreactive.
Electron shell structure 2, 8, 1 2, 8, 2 2, 8, 3 2, 8, 4 2, 8, 5 2, 8, 6 2, 8, 7 2, 8, 8
Electron sub-shell structure 1s22s22p6 1s22s22p6 1s22s22p6 1s22s22p6 1s22s22p6 1s22s22p6 1s22s22p6 1s22s22p6

Table 1 shows some trends across Period 3 (see Figure 1

3s1 3s2 3s23p1 3s23p2 3s23p3 3s23p4 3s23p5 3s23p6

trends are found in other periods. 185

1 2 3 4 5 6 7 0
1
2
3 Na Mg Al Si P S Cl Ar
4
5
6
7

▲ Figure 1 The Periodic Table with Period 3 highlighted

To understand how such atomic properties vary we have to understand all the forces
at play inside an atom.

3 4 5 6 7
luminium silicon phosphorus sulfur chlorine
2
Ne] 3s 3p1 2
[Ne] 3s 3p2 2
[Ne] 3s 3p3 2
[Ne] 3s 3p4 2
[Ne] 3s 3
 Forces that act on electrons in an
Periodic Trends 5
Forces that act on electrons in an atom
tom The forces that act on electrons in an atom
The forces that act on electrons in an atom are electromagnetic. They obey
Coulomb’s law, which states that the magnitude
are
of
Coulomb’s law, which states that the magnitude of the force between two chargedthe
electromagn
force betw
objects objects
is directly is directly
proportional toproportional
the product of to
their the product
charges and of
inversely their charg
. Theyproportional
obey to the square of the distance between their centres.
proportional to the square of the distance between their centres.
two charged
mathematically as:
and inversely force ∝ 2
q+q−
s is expressed r
where q+ and q− are the charges on the two objects and r is the
theirto:centres.
It simplifies

• Thecharges
opposite rules are: 1
attract; like charges repel

• ● opposite
the bigger charges
the charges, attract;
the stronger likeforce
is the charges repel
ance between
● the bigger the charges, the stronger is the force
• the further apart the particles, the weaker is the force
● the further apart the particles, the weaker is the force

This means that electrons are attracted towards the nucleus (F

greater the atomic number, the stronger is the force of attractio
are further away from the nucleus are attracted less than those clos
In addition, because they have –the same charge, electrons repel ea
Repulsion
they are more densely packed, the inner electrons repel outer elec
Attraction
–
+ repel each other.
than the other outer electrons
re 2.18). The
– Repulsion
Shielding
Electrons that and the effective nuclear charge
o the nucleus.
Effective nuclear charge across period 1
In a hydrogen atom, the nucleus has a charge of +1 and there is
ther. Because
1s-orbital. There are no forces of repulsion, so the electron feels
ns much more
attraction of Figure
a +1 2.18
charge. The forces acting
This means that electrons are attracted towards the nucleus. The greater the atomic
number,In
theastronger on
is thean electron
force of in
attraction. an atom
Electrons that are
helium atom, the nucleus has a charge of +2 and there further away from
are
the nucleus are attracted less than those closer to the nucleus.
the 1s-orbital. These electrons repel each other slightly. The res
force of attraction between the nucleus and each electron is
In addition, because they have the same charge, electrons repel each other. Because
sligh
between a +2 charge and one electron. Therefore, the helium
they are more densely packed, the inner electrons repel outer electrons much more
nucl
an eff ective nuclear charge of
than the other outer electrons repel each other. slightly less than 2.
electron in a
Effective nuclear charge across period 2
e full force of
The situation becomes more complicated for lithium and the remai
lithium, the nucleus has a charge of +3 and the outer 2s electron is
o electrons in
s that the net Key term
less than that
is said to have The effective nuclear
charge is the net charge
on the27nucleus, after
07404_C02_Edexcel_GF_Chem_009-036.indd
 Periodic Trends 6
7
Calculate the (6.63 × 10 −34 J s × 3.00 × 10 8 m s−1)
hc
Factors that effect the force
wavelength of attractionE on
(in m) = outer
λ
= electrons
600 × 10 −9 m
of electromagnetic
Nuclear charge 4.0 × 10 −17 J
radiation with = 1.2 × 102 p
When the nuclear charge becomes
a frequency of more positive (due to the 3.31presence of additional
× 10 −19 J/photon
protons), its attraction1368
on allkHz.
theDeduce
electrons increases.
which part of the Calculate the number of photons with wavelength
electromagnetic
Atomic Radius spectrum it belongs hc (6.63 × 10 −34 J s × 3.
For one photon: E = =
As the distance of theto.outer electrons from the nucleus increases, the λ attraction of 4 × 10 −9
the positive nucleus for the negatively charged electrons falls. 1
8 Calculate the So for one joule: = 2.01 × 1016
4.9725 × 10 −17
frequency of
Shielding Effect yellow light with
a wavelength of
The outer or valence electrons are repelled by all the other electrons in the atom in
1 Electron configuration
5800 × 10 −8 cm.
74 2 Atomic structure
addition to being attracted by the positively charged nucleus. The outer electrons are
9 The laser used to
shielded from the attraction of the nucleus Ionization
by the shielding energy
effect.
Explaining periodic patterns
read information
from a compact disc The first ionization energy
The third shell can hold a
is the minimum
However, when there are e
–
has a wavelength of one mole of isolated gaseous
shell thereatoms
is a to form
degree of o
st
–
780 nm. Calculate thermodynamic conditions. electronsFor
Atomic radexample,
enter the fourth the
the energy
required
associated with This electron does not
to bring about the
metals reaction:
beyond calcium the
–
feel the full effect of the positive the third shell until it con
– one photon of this
–
radiation. charge of theCl(g)
nucleus → Cl +(g) + e −
electrons. In addition, the
+ shells are divided into a nu
– The electron is removed from
(other than the outer sub-s
hydrogen) also
–
–
is, a 3p electron). Table 12.1
before gives
they cansome
form exam
chemi
–
energy, which is the enthalpy
This change
process is for the
called
the
These electrons IB the
shield Chemistry
outer dataAn important concept in
booklet.
electron from the nucleus 3 and also in Chapter 12
–
Table 12.1 Selected (Figure 2.50).Atomic
The electroradii
Element Ionization equation
ionization energies experience different attra
Oxygen O(g) → O + (g) + e −
■ Figure 2.50 Electron shielding presence of other electron
Sulfur S(g) → S + (g) + e −
experience the most shiel
Na Copper
1
– Cu(g) → Cu+(g) + e −
Figure 8.3 Periodici
ToK Link 10–
Jacob Bronowski: ‘OneFactors that affect
aim of the physical ionization
sciences has been to give anenerg
exact p
Across a What
One achievement… has been to prove that this aim is unattainable’. period,
are t
11+
for the aspirations of Values
natural of ionization
sciences in energies
particular and for depend
knowledge on
in the
genera f
This claim is probably relatedthe size of the
to ‘modern’ atom (orFrom
(approximately ion)
100 one
years old) atom
physics suo
special relativity and quantum physics, including the Uncertainty Principle. An exa
the nuclear
material or physical world is impossible.
charge
Quantum ●
mechanics the
means charge
that the of
wor
shielding
molecular level, and there arethe shielding
limits of effect.
experimental
electrons in precision dictated by the Unc
the atomic level is ‘schizophrenic’ due to its wave–particle
full shells ● the shielding r
duality. The material w
of scientific models, all of which are limited and incomplete as descriptions of phy

Figure
There is 8.4 Shielding
no absolute effect of
knowledge
Atomic
Across
inner and the scientific
in science method
radius
theassumes
periodth
of objects and phenomena existing out
shell electrons reduces the pull of the there that is As the
independent
increases of distance
the
andobserv
the
some physicists might question the assertion that the material world is indepen
nucleus in the outer shell. the attraction of
Schrödinger’s cat is both alive and dead until the observation is made, i.e. the b
Down
function is collapsed, and one of the eventualities – alive dead a falls. Tt
– isgroup,
orelectrons manifeste
10 Find out about the – ionization energ
thought experiment Niels Bohr wrote, ‘It is wrong to think that the task of physics is to find out how
‘Schrödinger’s Cat’ what we can say about nature.’
From one atom o
Nuclear charg
3+ nuclear ● the charge of
pull When the nucle
ToK Link
● presence
the shieldingof addii
–
Heisenberg’s Uncertainty Principle states that there is a theoretical limit to the p
increases. This c
–
can know the momentum and the position of a particle. What are the implicatio
Down the group
human knowledge?
Shielding
decreases andeffec
th
In 1927 the German physicist Heisenberg stated the Uncertainty Principle, which
dual behaviour of matter and radiation (de Broglie’s
repulsion from The
hypothesis). outer
It statesor val
that it
simultaneously the exact position and exact
innermomentum
shell of (orin the atom
velocity) of an in a
elect
particle) along a given direction.
electrons (’shielding’) nucleus. The ou
Mathematically,
Figure it can beforces
12.13 Electrostatic described by the equation:
operating on the the nucleus by t
ity

h
 Periodic Trends 7 nickel

Shielding and the effective nuclear charge

The effective nuclear charge is the net charge on the nucleus, after allowing for the
electrons in orbit around the nucleus shielding its full charge.
■ Electron arrangement and the periodic table
Effective nuclear charge across period 1
It is the electrons in the outer or valence shell that determine the chemical a
In a hydrogen atom, the nucleus has a charge of +1 and there is one
properties of the chemical element. The position of a chemical element in th electron in a 1s-
orbital. There are no forces of repulsion, so the electron feels the
related to its electron arrangement. The period number indicates the numbe full force of attraction
of a +1 charge.
atom of the element. All chemical elements in the same period have the sam
In groups 1 and 2, the number of valence electrons is equal to the
In a helium atom, the nucleus has a charge of +2 and there are two electrons in the group num
18, 1s-orbital.
the number of valence electrons is equal to the group number minus
These electrons repel each other slightly. The result is that the net force of 10.
Figure 3.6 shows how the 1
electron arrangement of a chemical element
attraction between the nucleus and each electron is slightly less than that between a
period number. This so-called ‘short form’ of the periodic table omits the
is re
trans
+2 charge and one electron. Therefore, the helium nucleus is said to have an
effective nuclear charge of slightly less than 2.
Group
1 2 13 14 15 16 17 18
Period 1 2
Effective
1 H nuclear charge across period 2 He
1 2
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
2,1 2,2 2,3 2,4 2,5 2,6 2,7 2,8
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
The situation
2,8,1 becomes
2,8,2 more complicated
2,8,3 2,8,4 for2,8,5
lithium and
2,8,6the remaining
2,8,7 elements. In
2,8,8
lithium, the
19 nucleus
20has a charge of +3 and the outer 2s electron is strongly repelled
by the
4 two Kinner 1sCa
electrons. The nucleus is shielded by the inner electrons and the
2,8,8,1
effective 2,8,8,2
nuclear charge is approximately +1. This is the +3 nuclear charge, minus
the effect of two negatively charged screening electrons.
Based on the electron arrangements of the elements (Chapter 12), the period
divided intoelement
The next four blocks of elements
is beryllium. (Figure
The nucleus has a3.7):
charge of +4, there are two 1s
■ electrons shielding the nucleus and two 2s electrons that also repel each other
s-block elements
slightly. Therefore, the effective nuclear charge is not exactly +2 (+4 nuclear charge
■ p-block elements
minus the effect of the two negative inner electrons) — it is slightly less than +2
d-blockofelements
■ because the extra repulsion by the two electrons in the outer orbit.
■ f-block elements.
The situation is slightly more complicated with the next element, boron. The atomic
number of boron is five (a nuclear charge of +5). There are two 1s electrons that
shield the outer electrons from the nucleus. The two 2s electrons are closer to the
nucleus than the single 2p electron and they repel it. Therefore, the effective
nuclear charge is significantly less than the +3 value predicted by the simplified
idea that effective nuclear charge is equal to the atomic number of the element minus
the number of inner-shell electrons.
1.
Periodic Trends 8

Electron arrangement and the periodic table

he electrons in the outer or valence shell that determine the chem
shielding
erties of the chemical
force element. The position of a chemical element
ed to its electron arrangement.
Li Be B TheCperiodN number
O indicates
F Ne the n
of the element. All chemical elements in the same period have th
oups 1 and 2, the number of valence electrons is equal to the group
he number of valence electrons is equal to the group number minu
electrostatic
igure 3.6 shows how the electron arrangement of a chemical elemen
attraction
d number. This so-called ‘short form’ of the periodic table omits the
towards
positive 1
nucleus
Group
1 2 13 14 15 16 17 18
d 1 Figure 12.15 A diagram illustrating how the balance 2
Similar arguments apply to other periods — the effective nuclear charge increases
1 H between shielding and nuclear charge changes across
across a period, but does not increase by as much as +1 between successive
He
1 period 2 electron 2 inner
elements. attracted
3 4 5 6 7 8 9 10 elect
by an shiel
creasesLithe force
2 Be of attraction
B C
on all the N electrons,
effective O so they F areNe valen
2,1 2,2 2,3 2,4 2,5 charge 2,6 2,711+ 2,8 elect
gly. Each additional electron across a periodofenters +1 the same from
11 12 13 14 15 16 17 18
increase in shielding is minimal (Figure 12.15). nucle
3 Na
for the
Mg
ionization
Al
energy to
Si
increase
P
across the
S period,
Cl there
Ar
2,8,1 2,8,2 2,8,3 2,8,4 2,8,5 2,8,6 2,8,7 2,8,8
energy19across 20 periods 2 and 3 (Figure 12.14). These dipssodium can
model Kof
4 electron electronic
Ca structure. inner
The core
core charge
charge = 11 –increase
10 = +1
od is the result of a change inelectrons
2,8,8,1
attracted 2,8,8,2 the sub-shell (sub-level) from
electrons
this electron of chlorine ther
by an shield the experiences
hangeeffective
in electron shielding. These valence have a than
greater
a does
effect
stronger the
than outer-shell
the
d on the electron
crease in atomic radius.
charge arrangements
11+ of the
In period 2, this firstthan
electron elements
attraction
decrease (Chapter
occurs
17+ 12), the p
of +1 Atomicthe radius decrease
ed into four blocks of
nd boron. When it is ionized,nucleus elements from the
(Figure 3.7):
the berylliumelectron atom
attraction(1s 22s 2 ) loses
experienced by
2 2 1 in sodium
m (1s 2selements
block 2p ) loses a 2p electron (Figure 12.16). More energy
are all in the third electris
m the lower energy 2s orbital in beryllium than from
increases, thethe higher
electrostat
-block elements sodium
ugh the 2score andcharge
electron 2pissub-levels
more
= 11 –diffi
10 cultareto in
= +1 the from
remove sameanthe shell,
argon the
nucleus
atom. energy
chlorine
Theincreases.
argon atom Th
-block
l (Chapterelements
is 2)
alsothat
this electron thethan
smaller energy gap between
the sodium shells
atom and, therefore,
core charge = 17 – 10 = +7
andthe sub-levels
outer
the nucleus and making electron is
experiences
closer to the nucleus and more strongly held.
Figurein3.2.8 Core2pcharge can be used to ex
in shell
block number.
elements. In addition, a single electron the sub-
a stronger
2 The
trends trend
within the in ionic
periodic table. radii is
y the inner electrons
attraction
17+ than the 2s electrons (Figure 12.17).
than the For the metals (sodium t
electron
in sodium
across the period. Silicon
4−
2p
(Si ) ion. For the non-me
3− • atomic radius decrease
(P ) to the chloride ion
• electronegativity increa (
chlorine
core charge = 17 – 10 = +7 radius • than
first the original
ionization energy
• ionic radius
negative ion has a larger decreases
Figure 3.2.8 Core charge can be used to explain of extra negative charges
trends within the periodic table.
ions have a larger radius
electron
Figure 3.2.9 Trends in properties across a p
The incr
• atomic radius decreases
The atomic radius is basically used to describe the size of an atom.fromThe left
Periodic Trends 9
Figure 8.3 Periodicity of atomic radii in the periodic table.
Effective nuclear charge in a group
The nuclear charge and the number of inner shielding electrons increase by the
Across a period, the atomic radius decreases from left to right (Figure 8.3).
same amount in a group. This leads to an assumption that the effective nuclear
From acting
charge one atom
on theofouter
an element
electronsto theelements
of the next acrossin theasame
period:
group of the
periodic
● the table hardly
charge varies,
of the but thisincreases
nucleus is a simplification of a more complex situation.

For the shielding

● instance, sodium remains the same
has 11 protons and, therefore, a nuclear charge of +11. It has
two electrons in the first shell and eight in the second shell. These ten
Across the period the effect of the nuclear charge on the outer electrons electrons
shield the outer, third-shell electron very
increases and the atomic radii decreases. efficiently and the effective nuclear
charge is close to +1 (+11 − 2 − 8 = +1).
Down a group, the atomic radius increases.
1
Potassium has 19 protons and, therefore, a nuclear charge of +19. The outer, fourth-
From one atom of an element to the next down a group:
shell electron is shielded from the nucleus by two electrons in the first shell, eight
● the charge
electrons of theshell
in the second nucleus increases
and eight electrons in the third shell, making a total of 18
inner shielding
● the electrons.
shielding From sodium to potassium, the number of protons has
increases
increased by eight and the number of shielding electrons has also increased by eight.
Down the group the effect of the nuclear charge on the outer
Therefore, potassium also has a similar effective nuclear charge close to +1.
electrons
decreases and the atomic radii increases.

Li Na K

outer electron outer electron outer electron

shielded by 2 shielded by 10 shielded by 18
inner electrons inner electrons inner electrons

Figure 8.5 Atoms of the Group 1 elements lithium, sodium and potassium.

Test yourself
1 Put the following elements in order of increasing atomic radius. Justify
your answers:
a) Mg, S, Si
b) Mg, K, Al
c) Si, Cl, K

30/03/15
ments of
Periodic Trends 10
Period 3
Atomic radius
Some
The key
radius of properties of atoms,
an atom is found such as
by measuring thesize and between
distance ionisationthe
−12 energy,
nuclei of are
two
1 pm = 1 × 10 m
periodic,
touching thatand
atoms, is, there are similar
then halving trends as you go across each period
that distance.
in the Periodic Table.
In general the atomic radius of an atom is determined by the balance between two
opposing factors:
Atomic radii
•These
radius
tell us effect
the shielding
of an
aboutbythe
isolated
thesizes
atom
of atoms.
electrons
because
Youshell(s)
of the inner
there is
cannot
Although
no clear is
measure
– this
it
makes the
not possible
point at
theatomic
to measure
which
radius larger. The shielding effect is the result of repulsion between the electrons
the an atomic radius for Ar, it is possible to
in electron cloud
the inner shell anddensity around
those in the outer orit valence
drops to zero. Instead half the
shell.
measure a value for the van der Waals’
distance between
1 pm = 1 × 10 centres
the −12
m of a pair ofradius
atoms is used, see Figure 1.
1
of this element.
• the nuclear charge (due to the protons) – this is an attractive force that pulls all the
The atomic radius of an element can differ as it is a general term.
electrons closer to the nucleus. With an increase in nuclear charge, the atomic
It depends
omic radius
on
decreases
the type
acrosssmaller.
of bond that
a period is basically the
it is forming – covalent, ionic,
radius becomes
metallic,
egativity van der
and ionisation energy Waals,
increase:and so on. The covalent radius is most
an increase
oss thecommonly
period but nousedsignifias
canta increase
measure of the size of the atom. Figure 2 shows a
in shielding.
plot
ne have theof
Atomic covalent
same number of
radius radius against
inner shells
decreases atomic
of electrons
across a number.
period
Although it is not possible
nt of shielding is similar); however, chlorine has to measure
Remember
(Even an atomic
that
metals canradius
effectiveform for
7+ whereas sodium has a nuclear charge of onlyAr,
nuclear it
covalentis possible
charge to
increases
molecules across
such the
as period.
Na inThis
themeans
gas
2
that the measure
outer-shell a value for
electrons the van
ofdo der
chlorine Waals’
therefore experience a greater
phase.
the outer Since
electrons arenoble
pulled gases
in more not in
strongly bond covalently with one attraction
another,to
radius of this element.
um andthe the
they atomic
nucleus
do not radius
than does
have is smaller.
the outer-shell
covalent radiielectron
and soofthey
sodium.
are often left out of
comparisons of atomic sizes.)
cally the
measure
ncrease
The of graph
the size shows
of an ion.that:
shielding.
• atomic radius is a periodic property because it decreases across each
nic radii
electrons of positive ions are smaller than
dii, and period
the ionic and
radii there
of is a jump
negative ions when
are starting the next period
has
eir
only atomic
• radii.
atoms get larger down any group.
ngly in
Why the
.10 (overleaf ) shows radii of atoms
a comparison of thedecrease
atomic and across a period
or theYou alkalican
metals. Each 1+this
explain ion istrend
smallerby than the
looking at the electronic structures of
formedthe (by loss
elements of an electron).
in a period, for example, sodium to chlorine in Period 3,
+
Na as it has one extra shell of electrons – the
as shown in Figure 3. +
on of Na is 2, 8, 1, whereas that of Na is 2, 8. Also,
Atomic
me nuclear radius
charge decreases
pulling in thefrom left
electrons to right
(11+), across
but period 3 due to the increasing
r than As you move from sodium to chlorine you are adding protons to the
unt ofattraction experienced
electron–electron by the
repulsion in outer-shell
Na, as there electrons. These outer-shell electrons are
ns are nucleus and electrons + to the outer main shell, which is the third shell.
paredallwith only
in the 10 in
third Na . The
electron electron
shell of thecloud
atoms; is however, as the effective nuclear charge
The charge
thanincreases,+
in Na , asthethere
on are
the
more
nucleus
electrons
increases
repelling
from +11 to +17. This increased
charge pulls electrostatic
the electronsattraction
in between
closer to the
the outer-shell
nucleus. electrons
There and
are the
no
charge pulling the electrons in.
tomic nucleus
and increases. This has the effect of pulling these outer-shell electrons in closer
additional electron shells tocanprovide
ive ions are larger than their parent atoms be seen more shielding. So the size of the
han tothethe nucleus and making the atom smaller.
atom decreases
es of halogen atoms with as you
their ionsgo(1−)across
in Figurethe period.
larger than Cl, because it has more electrons for the
he
and, therefore,
atom greater repulsion
Na between
Mg electrons.
Al Si P S Cl
, 8. Also, −
nd 17 protons in the nucleus. Cl also has 17 protons 2,8,5 2,8,6 2,8,7
(11+), but
has 18sizeelectrons.
of The repulsion between 18 electrons
s there
en 17 electrons,
atom so the electron cloud expands as an
oud is −
d to a Cl atom to make Cl .
epelling 2,8,1 2,8,2 2,8,3 2,8,4 2,8,5 2,8,6 2,8,7
atomic
(covalent)
an be seen 0.156 0.136 0.125 0.117 0.110 0.104 0.099
Figure radius / nm
ns for the
nuclear
ectrons. 11+ 12+ 13+ 14+ 15+ 16+ 17+
charge
7 protons
electrons
▲ Figure 3 The sizes and electronic structures of the elements sodium to chlorine
nds as an
 Periodic Trends 11

1
Summary: Across a period, the atomic radius decreases from left to right. From one
atom of an element to the next across a period:

• the charge of the nucleus increases

• the shielding remains the same

Across the period the effect of the nuclear charge on the outer electrons increases
and the atomic radii decreases.

Atomic radius
The radius of an atom is found by measuring the distance between the nuclei of two
touching atoms, and then halving that distance.

Trends across a period

Even though extra electrons are being added, the atoms get smaller going across
a period from left to right. From lithium to fluorine, the outer electrons are all
2
in the 2nd shell, being screened by the 1s electrons. The increasing number of
protons in the nucleus as you go across the period pulls the electrons in more
tightly. This is slightly offset by the increased repulsion of the electrons from each
other. However, the net effect is a decrease in radius (Figure 2.19). This pattern is
repeated in the 3rd period.
250
Atomic radius/pm

The
200 reason that atomic radius decreases across a period is basically the

same reason electronegativity and ionisation energy increase: an increase

150
in nuclear charge across the period but no significant increase in shielding.
Sodium
100 and chlorine have the same number of inner shells of electrons
(and hence the amount of shielding is similar); however, chlorine has
50
a nuclear charge
Li Be of B 17+C whereas
N O sodium
F Na has
Mg a Al
nuclear
Si Pcharge
S of only
Cl K Ca
11+. This means that the outer electrons are pulled in more strongly in
2nd period 3rd period
Figure 2.19 Trends in atomic radius
chlorine than in sodium and the atomic radius is smaller.
Trends in a group
Down a group, the trend is for atomic radii to increase steadily because of the
 244 12
Periodic Trends
262
Atomic radius increases down a group0
0 10 20
Down a group from top to bottom, atomic radii increase. In each new period the 30
270
outer-shell electrons enter a new energy level so are located further away from the At
nucleus. This has a greater effect than the increasing nuclear charge because of
ion of atomic radii in group 1 ■ Figure 3.20 Bar chart showing the va
shielding by the inner-shell electrons (effective nuclear charge stays nearly the
same.)
300

1Atomic radius/pm
200

Br
mber Atomic radius/pm 100 Cl
58
F
99
114
Summary: Down 133 a group, the atomic radius increases.
0 From one atom of an element
to the next down a group: 0 10 20 30
140
At
• the charge of the nucleus increases
The variation of ionic radius across a period is not a clear-cut trend, as
on ofthe
atomic radii in group 17 Figure 3.21 Bar chart showing the va
•the type of ion changes from one side to the other. Thus positive ions are
shielding effect increases
■
(effective nuclear charge stays the same)
formed on the left-hand side of the period and negative ions on the right-
•hand
Moving
increase
side.
in down
the numbera group,
of shells both the nuclear charge and the shiel
outer
Down the electrons
group the enter
effect of the new shells.
nuclear charge So,
on thealthough
outer the
electrons
For positive ions there is a decrease in ionic radius as the charge on nucleus
decreases gai
andfurther
the the away,
ionatomic butforalso
radii increases.
increases, but moreions
negative effectively screened
the size increases as thebycharge
an additio
increases (Figure 4.12).
+ 2+
Let us consider Na and Mg atomic: both ions
radii have
decreasethe same electronic
2+
configuration, but Mg has one more proton in the nucleus (Figure
4.13). Because there is the same number of electrons in both ions, the
amount of electron–electron repulsion is the same; however, the higher
2+
nuclear charge in Mg means that the electrons are pulled in more
atomic radii increase
strongly and so the ionic radius is smaller.

Ionic radii for ions of the same charge also increase down a
and 3.7). Ionic radii are the radii for ions in a crystalline ion
 Periodic Trends 13
How is atomic radius measured
We know that electrons in atoms are in located in atomic orbitals, which are regions of
Periodic
space where there is a high probability of finding an electron. This meansproperties
that the
position of the electron is not fixed, so we cannot measure the radius of the atom in
the same way as we measure the radius of a circle. One way of overcoming this
problem and finding the radius of an atom is to measure the distance between the
Figure 7.7 !
nuclei of two closest atoms of the element and dividing it by 2.
Periodicity in the first ionisation energies
of the elements.
The atomic radii of atoms can be obtained from X-ray analysis and electron density
maps. Using these techniques, it is possible to measure the distance between the

1
nuclei of atoms and then estimate the radius of individual atoms.

The atomic radius of an element can differ as it is a general term. It depends on the
typeArof bond that it is forming – covalent, ionic, metallic, van der Waals, and so on.
group 0
The atomic radii of metals are obtained by measuring the distance between the
Cl nuclei of neighbouring atoms in metal crystals. The atomic radius is simply half of the
inter-nuclear distance. This is sometimes referred to as metallic radius.
S

Ca
group 2
group 1
K

8.3
20
More trends in the proper
the elements of Period 3
Learning objectives: Some key properties of atoms, such as
➔ Describe the trends in atomic periodic, that is, there are similar trend
anyThe
pattern
atomic radiiand
radius of non-metals in the Periodic Table.
first ionisationare obtained from the distance between the nuclei
ds 2
of and energyjoined
similar3.atoms of thebyelements in bond. So, for non-metals, the atomic radius is
a covalent
half of
s decrease the Period 3.
covalent bond length. Because of Atomic
this link to radii
covalent bonds, the atomic
Data
? radii of
➔ Explain
non-metals these
are trends.
sometimes called These
covalent tell
radii. us about the sizes of atoms. Y
Specification reference: 3.2.1 radius of an isolated atom because ther
the electron cloud density around it dr
distance
atomic between the centres of a pair o
radius
The atomic radius of an element can di
molecules. Chemists use It depends on the type of bond that it i
distance betweenr the metallic, van der Waals, and so on. The
commonly used as a measure of the siz
be defined precisely plot of covalent radius against atomic n
number of bonds.
(Even metals can form covalent molecu
nces between atoms in non-metallic molecule
phase. Since noble gases do not bond c
n-metals▲are
Figurecalculated
1 Atomic radii are taken to be they do
atomic radius not have covalent radii and so
half the distance between the centres of
ules (covalent radii).
a pair of atoms
comparisons of atomic sizes.)

d. Across the period Na The graph shows that:

99 nm forHint
chlorine. From • atomic radius is a periodic property
Periodic Trends 14
How is atomic radius measured
In the simple molecular structures of non-metals, one molecule touches the next and
it is sometimes useful to compare the distances between neighbouring atoms which
are not chemically bonded. This distance in non-metal crystals is called the van der
Waals radius.

Consider a group of gaseous argon atoms. When two argon atoms collide with one
another there is very little penetration of their electron cloud densities. Argon does not
form a diatomic species. If argon is frozen in the solid phase the atoms would touch
3.2 PE
each other but would not be chemically bonded. In this case the distance between
the argon atoms could be measured and hence non-bonding atomic radius. The
atoms could be measured and hence Rnb could be found (figure 2). The
non-bonding atomic radius is often termed the van der Waals’ radius.
non-bonding atomic radius is often termed the van der Waals’ radius

d = 2Rnb
▲ Figure 2 Atoms of argon in the solid phase. The atoms are touching but not chemically
bonded. The non-bonding atomic radius of argon Rnb is 188 pm (d = 376 pm)

Section 9 of the Data booklet provides data for the covalent atomic radii
of the elements. The general term “atomic radius” is used to represent
the mean bonding atomic radius obtained from experimental data
over a wide range of elements and compounds. Note that the bonding
atomic radius is always smaller than the non-bonding atomic radius. Th
approximate bond length between two elements can also be estimated
from their atomic radii.
For example, for the interhalogen compound BrF:
atomic radius of bromine = 117 pm
atomic radius of fluorine = 60 pm
bond length of Br-F = 177 pm
Compare this with the experimental bond length of Br-F in the gas
 chemical properties across periods and down grou
Periodic Trends 15
First ionization energy
The Data booklet provides data for the atomic radii of the elements. The general term
The first ionization energy is the minimum energy
“atomic radius” is used to represent the mean bonding atomic radius obtained from
req
from one mole of gaseous atoms (under standard therm
experimental data. Note that the bonding atomic radius (metallic and covalent) is
In general:
always smaller than the non-bonding (van →
atomic radiusX(g) derX +(g) + e
Waals). −

For example, the first ionization energy of hydrogen is g

0.20 H(g) → +
H (g) + e− ∆H = +1310 kJ mol−1
Na Ar
The amount of energy required to carry out this proces
1310
Mg kilojoules.
Period 3
Atoms of each element have different values of first
Al

1
Electronegativity
atomic radius/nm

Si
The electronegativityPof an atom S
is the ability or powe
0.10
shared pairs of electrons to itself. The greater the electr
Cl

ability to attract shared pairs of electrons to itself.

Electronegativity values are usually based on the Paul
the most electronegative atom. The least electronegative
value of 0.7. The values for all the other elements lie betw
electronegativity values are pure numbers with no units.
0
11 12 ■ Trends
13 14in the
15 properties
16 17 of the
18 elem
group 17 proton number

Phosphorus, sulfur and chlorine all form small covalent molecules, P4, S8 and
Trends in atomic and ionic radii
Cl2 respectively. When these substances melt, it is only necessary to break weak
a and notAt
intermolecular bonds
10_04 Cam/Chem AS&A2 the interatomic
strong right of theattractions.
periodicThetable, the atomic
melting points radius is d
decreaser in the order sulfur >nuclei of
phosphorustwo > covalently
chlorine (seebonded atoms
Figure 10.5), the(Figure 3.19). Fo
Barking Dog Art
intermolecular bonds becoming weaker as the molecules become smaller.
molecule (the distance between two chlorine nuclei) is
r
The melting point of argon is low, as the attraction between the argon atoms is −1
of chorine is ½ × 199 = 99 pm (1 picometre [pm] = 10
very small.
left of the periodic table, the atomic radius is that of th
radius). For the noble gases the atomic radius is that of
radius).
metallic radius
In general the atomic radius of an atom is determin
b factors:
r r ■ the shielding effect by the electrons of the inner sh
larger.V The
Cr shielding effect is the result of repulsion

Si and
Sc
Ti those in the outer or valence shell.
Fe Co Ni
covalent radius
■ the nuclear charge (due to the protons) – this is an
Cu
c closer to the nucleus. With an increase in nuclear c
Mn Ge

Ca
Mg
Al
r
However, when moving downZna group in the periodic t
S
radius as the nuclear charge increases (Tables 3.4 and 3
Na P Se
Cl
Ar
K
result of two factors: Ga As
Br
F van der Waals’ radius Kr
Ne ■ the increase in the number of complete electron sh
(for group 18)
9 10 11 12 13 14
and the nucleus
15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
■ Figure 3.19
■ the increase in the shielding effect of the outer elec
proton number
Atomic radius
h
Electrical conductivity
Sodium, magnesium and aluminium are metals. They have delocalised electrons that
are free to move in the lattice of cations (see section 4.11). Silicon is a semiconductor.
The other elements in the third period form covalent bonds with no free electrons,
 Periodic Trends 16A negative ion is always larger than its neu
Periodic Trends in negativeionic radiusion, an atom must gain one or more
The radii of cations andthe same
anions atomic
vary from number,
the parent atoms fromsowhich
forces
they of
are attracti
formed in the following is extra repulsion due to the increased numbe
way.

causes the ion to expand, moving

The radii of cations are smaller than those of their parent atoms. The reason the elect
for this is that there are once again,
more protons thanthere
electronsisinathebalance between
cation so the valence the f
electrons are more stronglyrepulsion.
attracted to the nucleus.

Na Na+ Cl
Ion Atomic number Ionic radius/pm Ion Atomic number Ionic radius/pm
Li+ 3 68 F– 9 133

Electron affinity (EA)

If an atom loses all its outer electrons, the radius of the resulting ion17is much smaller181
Na + 11 98 Cl –

+
than the atomic19radius. This is because:
K 133 Br– 35 196
I–
•
Rb+ 37 148 353 219
there is one fewer shell of electrons
Electron affinity can be represented by the eq
Cs + 55 167 At– 85 No data

• there are
Fr+fewer electrons
87 in the positive
−
A(g) + e → A (g)
ion than
−
in the atom, so
No data the electron– ■ Table 3.7 The variation of ionic radii in group 17
■
electron repulsion is less, causing a further
Table 3.6 The variation of ionic radii in group 1
reduction in the radius.

The negatively charged electron being adde

charged nucleus. There is a force of attracti
energy is released when the two are brought c
+ + +
Li Li Na Na K K
The first electron affinity of oxygen is −14
per mole, for the process:
O(g) + e− → −
O (g)
Trends in first ionization energy
On moving down a group, the atomic radius increases as additional electron shells are added. Th
The second electron affi nity can be represe
causes the shielding effect to increase. The further the outer or valence shell is from the nucleus
the smaller the attractive force exerted by the protons in the nucleus. Hence, the more easily an
−
Aand(g) − 2−
e the→ionization
outer electron can be removed the +
lower A (g) energy. So, within each group, the
first ionization energies decrease down the group. This is shown in Table 3.8 and Figure 3.24.
The second Li
electron affi nity of an element is a
First ionization
mber energy/kJ mol –1 energy is required to add an electron to an
500 Na
–1
First ionization energy/kJ mol

519 electron
400 is repelled
K
by theRb negative ion. The
Cs
494
418
bring the ion and the electron together.
300
402
376 200

on of first ionization
100

0
0 10 20 30 40 50 60
Atomic number
 Periodic Trends 17
charge increases from 11 to 12 to 13. The force of attraction
For ions with the same electron configuration (e.g. Na , Mg and Al ), the ion
+ 2+ 3+ between
f the aluminium ion (13 protons) and its ten
with the greatest charge will have the smallest radius. electrons is, therefore,
hat between the nucleus of the other ions and their ten electrons. This
3+ ion
Thetonuclear
havecharge increases radius.
the smallest from 11 to 12 to 13. The force of attraction between the
nucleus of the aluminium ion (13 protons) and its ten electrons is, therefore, greater
than that between the nucleus of the other ions and their ten electrons. This causes
egative ions
the Al3+ ion to have the smallest radius.
on is always larger than its neutral atom (Figure 2.20). To form a
The radii of anions are larger than those of their parent
an atom must gain one or more electrons. The atom and the ion have atoms. A negative ion is
always larger than its neutral atom. To form a negative ion, an
mic number, so forces of attraction remain the same. However, there atom must gain one or
more electrons. The atom and the ion have the same atomic number, so forces of
sion due to the increased number of electrons in the same shell. This
1
attraction remain the same. However, there is extra repulsion due to the increased
n to expand, moving the electrons further from the nucleus until,
number of electrons in the same shell. This causes the ion to expand, moving the
here is a balance between the forces of attraction and the forces of
electrons further from the nucleus.

Na+ Cl Cl –

n affinity (EA)
ity can be represented by the equation:
→ −
A (g)
ly charged electron being added is brought towards the positively
eus. There is a force of attraction between the two and, therefore,
ased when the two are brought closer together.
ctron affinity of oxygen is −1
−142 kJ mol . This is the energy change,
the process:
The variation of ion
−
→ O (g) the type of ion change
electron affinity can be represented by the equation: formed on the left-ha
− → A 2−(g) hand side.
Table 2.6 Atomic and ionic radii For positive ions th
lectron affinity of an element is always positive
Group 1 Group 2 Group 3 Group 4 Group
(endothermic)
the
5 ion
because
Groupincreases,
6 Group 7 but f
uiredAtomic
to add anNaelectron to an already negative ion.
N increases
The incoming
Mg Al C O (Figure
F 4.12
pelledRadius/pm
by the negative ion. Therefore, energy has to be supplied to +
186 160 143 70 65 Let us consider Na
60 50
and the electron together.
Ionic Na+ Mg2+ Al3+ N3− confiOguration,
2− F− but Mg
Radius/pm 95 65 50 171 140 136
4.13). Because there is
amount of electron–el
The nuclear charge increases from 11 to 12 to 13. The force of attraction between Io
the nucleus of the aluminium ion (13 protons) and its tennuclear charge
electrons is, in Mg
therefore, s
Periodic Trends 18

1
Increasing electronegativity and first ionization energy

1310 Increasing electronegativity and first ionization energy 2370

H He
2.1
519 900 799 1090 1400 1310 1680 2080
–
(O +844)
Li Be B C N F Ne
O
1.0 1.5 2.0 2.5 3.0 3.5 4.0
494 736 577 786 1060 1000 1260 1520
–
(S +532)
Na Mg Al Si P Cl Ar
S
0.9 1.2 1.5 1.8 2.1 2.5 3.0
418 590 632 661 648 653 716 762 757 736 745 908 577 762 966 941 1140 1350
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.8 1.9 1.6 1.6 1.8 2.0 2.4 2.8
402 548 636 669 653 694 699 724 745 803 732 866 556 707 833 870 1010 1170
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
0.8 1.0 1.2 1.4 1.6 1.8 1.9 2.2 2.2 2.2 1.9 1.7 1.7 1.8 1.9 2.1 2.5
376 502 540 531 760 770 762 841 887 866 891 1010 590 716 703 812 920 1040
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.2 2.2 2.2 2.4 1.9 1.8 1.8 1.9 2.0 2.2
181 510 669
Fr Ra Ac First ionization
–1
0.7 0.9 1.1 energy (kJ mol )

Element

Electronegativity

Figure 3.2.1 Electronegativity and first ionization energy values, showing trends within the periodic table. A similar table can be found in the IB Data Booklet © IBO 2007.

30 Decreasing atomic and ionic radii

H He
154 (1–)
Increasing atomic and ionic radii

152 112 88 77 70 66 58
Li Be B C N O F Ne
68 (1+) 30 (2+) 16 (3+) 260 (4–) 171 (3–) 146 (2–) 133 (1–)

186 160 143 117 110 104 99

Na Mg Al Si P S Cl Ar
98 (1+) 65 (2+) 45 (3+) 42 (4+) 212 (3–) 190 (2–) 181 (1–)
271 (4–)
231 197 160 146 131 125 129 126 125 124 128 133 141 122 121 117 114
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
133 (1+) 94 (2+) 81 (3+) 90 (2+) 88 (2+) 63 (3+) 80 (2+) 76 (2+) 74 (2+) 72 (2+) 96 (1+) 74 (2+) 62 (3+) 53 (4+) 222 (3–) 202 (2–) 196 (1–)
68 (4+) 59 (5+) 60 (4+) 64 (3+) 63 (3+) 69 (2+) 272 (4–)
244 215 180 157 141 136 135 133 134 138 144 149 166 162 141 137 133
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
148 (1+) 110 (2+) 93 (3+) 80 (4+) 70 (5+) 68 (4+) 65 (4+) 86 (2+) 126 (1+) 97 (2+) 81 (3+) 112 (2+) 245 (3–) 222 (2–) 219 (1–)
71 (4+)
262 217 188 157 143 137 137 134 135 138 144 152 171 175 170 140 140
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
167 (1+) 34 (2+) 115 (3+) 81 (4+) 73 (5+) 68 (4+) 67 (4+) 66 (4+) 137 (1+) 127 (1+) 95 (3+) 120 (2+) 120 (3+)
85 (3+) 110 (2+) 84 (4+)
270 220 200
Fr Ra Ac Atomic
radius
(10–12 m)

Element
Ionic
radius
(10–12 m)

Figure 3.2.2 Atomic and ionic radii values showing trends within the periodic table. A similar table can be found in the IB Data Booklet © IBO 2007.
 Periodic Trends 19
Skill Check 1
ne
First particle >, =, < Second particle
−
a Chlorine atom (Cl) Chloride ion (Cl )
3+
b Aluminium ion (Al ) Aluminium atom (Al)
c Calcium atom (Ca) Sulfur atom (S)
+ −
d Sodium ion (Na ) Fluoride ion (F )
2+ 2+
e Magnesium ion (Mg ) Calcium ion (Ca )
2− +
f Sulfide ion (S ) Potassium ion (K )

1
EMENTS AND THEIR OXIDES
iodicity within groups and periods,
ents and some of their compounds.
n arrangement of the elements.

group
eactive nature. Their tendency to 3.3.1
that they must be stored under Discuss the similarities and
in secondary school laboratories differences in the chemical
olent reaction with water. properties of elements in the
same group. © IBO 2007
er increases down group 1. While
ter and reacts slowly, producing
ently, whizzing around on the
gas in what is sometimes described

g its progress on the surface of the

.1). The white smoke in figure 3.3.1
. Potassium burns spontaneously

olution when they react with water.

Figure 3.3.1 Sodium will burn with a yellow flame

if its motion on the surface of water is stilled.
en in figure 3.3.1. Phenolphthalein
e the reaction with sodium and has
ydroxide.
by the decrease in electrostatic
and the positive nucleus of the
 factor is Trends
Periodic the increase
20 in the atomic radius, making the outermost electro
from the nucleus and so easier to remove.
Periodic trends in ionisation energy
The general trend across a period is for the first ionisation energy to
The first ionisation energies of the elements show periodicity. The
However, there are a number of slight variations from this trend. pattern from
lithium to neon is repeated exactly with the elements sodium to argon. Apart from the
Figure 2.6 shows that there are maxima at each noble gas and minima
insertion of the d-block elements, this pattern is seen again from potassium to at e
1 metal.
rubidium. There are dips after the second and fi fth elements in both period

2400
1st ionisation energy/kJ mol–1

He
Why
2200the radii of atoms
Ne increase down a group
Going
2000 down a group in the Periodic Table, the atoms of each ele
have one
1800
one1600
extra complete
F
main shell of electrons compared with
before. So, for example, inArGroup 1 the outer electron in sod
1
is in main shell N3, whereas in potassium it is in main shell
Kr
4. So
1400
down the group, the outer electron main shell is further from th
O Cl
1200 H
nucleus and the atomic radii
P increase. Br
1000 C As
Be Zn
S
Se
First ionisation
B energy
Si 800 Mg
Ge
600
The first ionisation energy
Al is the energy required to convert a m
Li Na Ga
isolated gaseous atoms into a mole
400
K of singly positively charged
Rb g
ions, that is, to remove one electron from each atom.
200

0 + –
E(g)
0 ➝ E
5 (g) +
10e (g)15 where
20 E
25 stands
30 for any
35 elemen
40
Atomic number
The first ionisation energies also have periodic patterns.
Figure 2.6 Variation of the first ionisation energy with atomic number These ar
shown in Figure 4.

2500 He

Ne
–1
first ionisation energy / kJ mol

2000

F
Ar
1500 N
02_Edexcel_GF_Chem_009-036.indd 17
O Cl
H
1000 P
Be C
Mg Si S
B Ca
500 Al
Li Na
K
0
0 5 10 15 20
atomic number

▲ Figure 4 The periodicity of first ionisation energies

 Periodic Trends 21 3.2 Periodic trends 101

The Ions
general trend
of sodium, across and
magnesium a period is forare
aluminium the first ionisation
isoelectronic energy
species (Table to increase.
3.15). The nuclear
2 2 6
In Figure
charge increases2, notice
from the ion
the sodium small
to thedrop between
aluminium ion. The phosphorus (1s , pulls
higher nuclear charge 2s ,all 2p ,
• the
3s 2
electron
, 3p 3shells
) and closer to
sulfur the(1s 2
nucleus.
, 2s 2
Hence,
, 2p 6the
, 3s
As the effective nuclear charge increases from left to right
2
ionic
, 3p 4
radii
).decrease.
In phosphorus,
across a periodeach of the
Similarly, the nuclear charge increases from the phosphide ion to the chloride ion. The
three 3p orbitals contains just one electron, while in sulfur, one of the
8.3 (nuclear
More nuclear
higher charge
trends incharge increases
the properties and
of the
causes the the
elements
electron shielding
shellsofto effectively
Period 3
be pulled remains the same), the
closer to the nucleus. Again, the
3p
ionic orbitals
radii decreasemust
(Table contain
3.16). two electrons. The repulsion
valence electrons are pulled closer to the nucleus, so the attraction between the between these
paired
Species
electrons
Na
makes
electrons and the nucleus
+ Mg
it
2+ easier
increases.
Al3+ to
This remove
makes
Species it one
more of them,
difficult
P 3– to despite
remove
S 2– an the
Cl –
The first ionisation energy generally increases across a period
increase in nuclear
electron from the atom.
Nuclear charge +11 charge,
+12
(see see
+13
Figure Figure
4), 4.
Nuclear
alkali charge
metals +15 and lithium,
like sodium, Na, +16 Li,+17
have the
Number of electrons 10 lowest values
10 10 and Number
the nobleofgases (helium,18He, neon,18Ne, and18
electrons argon,

•
Ar) have the highest values.
Atomic
Ionic radii decrease
radius/pm 98 across
65 a period
45 – because the distance212
Ionic radius/pm between
190the 181
2p ionisation energy decreases going3pdown any group. The
The first
■ valence
Table 3.15 electrons
1s 2s and
Atomic data the nucleus
for sodium, fordecreases,
magnesium
trends it3sGroup
Table
Group■1 and becomes
3.16 Atomic more difficult
data for
0 are shown in to
redremove
phosphide,
dotted sulfide
and green,
and aluminium ions andgraph.
chloride ions
an electron from the atom. respectively on the
The large increase in size from theYou
of an additional
orbitalselectron shell.inThis
(sub-shells)
aluminium
causes5).
phosphorus
(Figure
ion these
can explain
1
to thepatterns
phosphide ion is due
by looking to the presence
at electronic arrangements
a large increase in the shielding effect and as a result
However, there are a number of slight variations from this trend.
the ionic radius increases. easier
Outer electrons are harder to remove as nuclear charge
2pincreases 3p to lose
Trends in 1s
first ionization
2s energy 3s
The first ionization energies of the elements in period 3 are listed in Table 3.17. The general
11+ 12+ 13+ 14+ 15+ 16+ 17+ 18+
trend is an increase in first ionization energy across the periodic table. When moving across
a period from left to
orbitals right the nuclear
(sub-shells) in sulfurcharge increases but the shielding effect only increases
[Ne]3s1 [Ne]3s2 [Ne]3s2 3p1 2 3p2
slightly (since electrons enter the same shell). Consequently, the electron shells are pulled
[Ne]3s [Ne]3s 2 3p3 [Ne]3s 2 3p4 [Ne]3s2 3p5 [Ne]3s 2 3p6

▲progressively closer to
Figure 5 The electronic the nucleus
structures and as sodium
of the elements a resultto first
argonionization energies increase.
▲ Figure 4 Electron arrangements of phosphorus and sulfur
Element Sodium Why the first
Magnesium ionisationSilicon
Aluminium energy increases Sulfur
Phosphorus across aChlorine
period
First ionization energy/ As you
736go across 577
494 a period from
786 left to 1060
right, the number
1000 of1260
protons
Both these cases, whichin go
kJ mol –1 against
the nucleus the expected
increases trend,
but the electrons aresame
enter the evidence
main shell,
that confirms the existence of 5.s-The
see Figure and p-sub-shells.
increased charge on theThese
nucleus were
means that it gets
However, the increase in first ionization
Down a group energydifficult
increasingly is not uniform
to removeandanthere are two decreases –
electron.
Thepredicted
trend
between by
magnesium quantum
down aand group theory
is for and
aluminium and
thebetween the
first ionisation Schrödinger
phosphorusenergy equation.
toThese
and sulfur. decrease.
decreases can
Down
only
Hint be a group,
explained the
by ionisation
reference to Why energy
the
sub-shells first
and decreases.
ionisation
orbitals. energy decreases going down a group
Although the number of protons increases, so does the number of down
shielding
Trends in ionisation energies down a group in the
The number
The first ionization energy of aluminium is lower of filled inner
than that shells
of increases
magnesium, even the
thoughgroup. This
The
Filled first
inner
electrons,
aluminiumhence ionisation
electron shells are
keeping
has a smaller energies
saidtheradius.
atomic (kJ
results
effective mol
in an –1
)
nuclearin
The decrease of
increase the
in
charge elements
shielding. Also,
constant.
first ionization in
theGroup
electron
Thefrom
energy main 1
to of
be the
removed
factor is
magnesium
is
(1sPeriodic Table
to shield electrons in the outer at an6 increasing distance from the nucleus and is therefore held less
periodic
the
2 2s 2p table
2
increase
6 2
3s in
) totheare shown
aluminium
atomic
shell from the nuclear charge.
(1s2 in
2s
radius,
2 Table
2p 3s
making
2 8.6.
3p1)
theoccurs because
outermost the electrons
electron in the
further filled
from
strongly. Thus the outer electrons get easier to remove going down a
3s
the
orbital are more effective at shielding the electron
group because theyin theare3pfurther
orbitalaway
thanfrom
they the
are nucleus.
at shielding each
nucleus
Figure
Table and
8.6 5 so
First easier
shows
ionisation
other. Therefore less energy is to
thatremove.
thereto
energies
needed ofisthea Group
removegeneral decrease
1 elements.
a single 3p electron thanin tofirst ionisation
remove a paired 3s
electron. Why there is a drop in ionisation energy from one period
energy
Element going down Group 2,
Li and the
Na same Kpattern is
Rb seen in
Cs other
to the 2next
2 6 2 2 1 1
The first ionization energy of sulfur (1s 2s 2p 3s 3p 3p 3p ) is less than that of phosphorus
groups.
(1s2 2s2 2p6 3s2This
3p13p 1is
3p
because
1) because
the
Moving
less
outer
from electron
neon in Period is
0 in
(far a main
right) with shell
electronthat gets
arrangement
4
–1 energy is required to remove an electron from the 3p orbitals
First ionisation energy/kJ mol2,8 to520 sodium,
496
2,8,1
419 403 376
(Period 1, far left) there is a sharp drop in the
further from the nucleus in each case.
of sulfur than from the half-filled 3p orbitals of phosphorus. The presence of a spin pair of electrons
first ionisation energy. This is because at sodium a new main shell
results in greater electron repulsion compared to two unpaired electrons in separate orbitals.
starts and so there is an increase in atomic radius, the outer electron is
Factor 1 Atomic radius further – increases down the group and the outer
from the nucleus, less strongly attracted and easier to remove.
■ Trends electron
in electronegativity
is further from values
the nucleus. This tends to decrease
900 Be
The electronegativities of the elements
the ionisation energy in period
as we3 are
go listed
down in Table
the 3.18.
group.The general trend
is an increase in first ionization Summary questions
energy across the periodic table. When moving across a period
850
–1

from left to
Factor 2 right the nuclear
Nuclear charge increases
charge – but thedown
increases shielding
the effect only increases
group. This slightly
tends toacross a
1 What happens to the size of atoms as you go from left to right
first ionisation energy / kJ mol

(since electrons enter the same shell). Consequently, the electron shells are pulled progressively
800 increase the ionisation period? Choose
energy fromas
increase,
we decrease,
go down no change.
the group.
closer to the nucleus and as a result electronegativity values increase.
2 What happens to the first ionisation energy as you go from left to right
Mg
Factor
Element 3
750 Shielding effect – increases down the group. This reduces
across a period? Choose from increase, decrease, no change.
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine
the effect of the 3 nucleus.
What happens to the
This nuclearto
tends charge of the atomsthe
decrease as you go left to right
Electronegativity 0.9 1.3 1.6 1.9 2.2 2.6 3.2
nts 700 across a period?
ionisation energy4 as we go down the group.
Why do the noble gases have the highest first ionisation energy of all
Generally, the electronegativity values of chemical elements increase across a period and
650 the elements in their period?
decrease down
Factors 1 and a group (Figure 3.28).
3 outweigh This observation
factor can be used
2 as ionisation to compare
energy the relative
decreases down
electronegativity values of two elementsCa in the periodic table. To do this, find the positions of
a group.
600
154 Sr
Across550a period
Across a period, ionisation energy increases. This is illustrated in Ba Table 8.7.
500
0 ionisation
Table 8.7 First 10 energies20 of elements 30in Period 2. 40 50 60
01 atomic number 18/0
B C N O F Ne
▲ Figure
801
5 The first
1086
ionisation energies
1402
of the elements
1314
of Group
1681
2 2081
 8.4 A closer look at ionis
Periodic Trends 22
Why there is a drop in ionisation energy from one period to the next
Moving from neon in Period 2 Group 18 (far right) with electron arrangement 2,8 to
sodium, 2,8,1 (Period 3 Group 1 far left) there is a sharp drop in the first ionisation
This chapter revisits the trends in ionisation energies first
energy. This is because at sodium a new main shell starts and so there is an increase dealt wi
in Topicradius,
in atomic 1.6, the
in outer
the electron
context of periodicity.
is further Theless
from the nucleus, graph of attracted
strongly first ionisa
energy
and easieragainst
to remove.atomic number across a period is not smooth. Figu
below shows the plot for Period 3.
A closer look at ionisation energies of Period 3

1750 Group 0
Ar
1500 1
–1

Group 7
first ionisation energy / kJ mol

Cl
1250
Group 5
P
1000
Group 2 Group 6
Mg S
750 Group 4
Group 1 Si
Na
500 Group 3
Al
250

0
10 11 12 13 14 15 16 17 18
atomic number
▲ Figure 1 Graph of first ionisation energy against atomic number for
Theelements
the graph of first
of ionisation
Period 3 energy against atomic number across a period is not
smooth. It shows that:
It shows that:
the first ionisation energy actually drops between Group 2 and Group 13, so that
•aluminium has aionisation
the first lower ionisation energy actually
energy than magnesium
drops between Group 2 and
Group 3, so that aluminium has a lower ionisation energy than
the ionisation energy drops again slightly between Group 15 (phosphorus) and
magnesium
Group 16 (sulfur).
• the ionisation energy drops again slightly between Group 5
Similar patterns occur in other periods.
(phosphorus) and Group 6 (sulfur). You can explain this if you look at the electron
arrangements of these elements.
Similar patterns occur in other periods. You can explain this if you
look at the electron arrangements of these elements.

The drop in first ionisation energy between

Groups 2 and 3
For the first ionisation energy:
• magnesium, 1s 2 2s2 2p6 2
3s , loses a 3s electron
• aluminium, 1s 2 2s2 2p 6 3s 2 1
3p , loses the 3p electron.
 Specification reference: 3.2.1
Periodic Trends 23 3p

3s
The drop in first ionisation energy between Groups 2 and 3

energy
actually
For thedrops betweenenergy:
first ionisation Group 2 and 2p
m has Hint
a lower ionisation energy than 2s
•
magnesium, 1s2 2s2 2p6 3s2 , loses a 3s electron
Ionisation energies are sometimes
ps again slightly between Group 5
•
aluminium,
called
6 (sulfur). 1s
ionisation
2 2s 2p 3s 3p
enthalpies.
2 6 2 1 , loses the 3p 1s
electron

2 2s2 2p6 3s2

er periods. You can
The p-electron explaininthis
is already if you
a higher energy level than the s-electron, so it takes less
magnesium 1s
ments of these
energy elements.
to remove it

ation energy between complete removal complete removal

1st IE 1 1st IE

y: 3p 3p
2, loses a 3s
3s electron 3s
energy

energy
2 1
3p , loses the 2p
3p electron. 2p

higher 2s
energy
level than the s-electron, 2s
rgies
ove it, see Figure 2.
1s 1s

The drop in first

2 2 ionisation
6
magnesium 1s 2s 2p 3s2 energy between 2 2 6
aluminium 1s 2s 2p 3s 3p 2 1

Groups 5 and 6 ▲ Figure 2 The first ionisation

The drop in first ionisation energy energies
between of
Groups magnesium
15 andand
16 aluminium
An electron in a pair will be easier to remove that one in an orbital
complete removal (not to scale)
Anonelectron
its ownin abecause
pair will be
it easier to remove
is already thatrepelled
being one in an by
orbital
theonother
its own because
electron.
itAs shownbeing
is already in IEFigure
1st repelled3:by the other electron.
155
• 3p 2 2 2
• phosphorus, 1s 2s2 2p6 3s2 3p3, as no paired
phosphorus, 1s 2s 2p 6 3s 2
has electrons
no paired 3
3p ,
electrons in a
in a p-orbital because
p-orbital
each because each p-electron
3sp-electron is in a different orbital is in a different orbital
energy

• sulfur, 2p 1s 2 2s2 2p 6 3s 2 4
3p ,
has two of its p-electrons paired in a
• sulfur,
2s
1s2 2s2 2p6 3s2 3p4, has two of its p-electrons paired in a p-orbital so one of
p-orbital so one of these will be easier to remove than an unpaired
these
onewillduebeto
easier
thetorepulsion
remove thanofan
theunpaired
other one due to in
electron thethe
repulsion
sameoforbital.
the
other electron in the same orbital.
1s

2 2 6
2p
2 1
3p
1s aluminium
2s 1s 2s 2p 3s 3p 3s
▲ Figure 2 The first ionisation
energies of magnesium and aluminium
orbitals (sub-shells)
(not to scale) in phosphorus
easier
2p 3p to lose
1s 2s 155 3s

orbitals (sub-shells) in sulfur

▲ Figure 3 Electron arrangements of phosphorus and sulfur

Successive ionisation energies

If you remove the electrons from an atom one at a time, each one is
harder to remove than the one before. Figure 4 is a graph of ionisation
 hence there is a
Periodic Trends 24
greater attraction (higher effective nuclear charge) fo

s sub-shell s sub-shell s sub-shell

He
filling up the
Ne filling up the
p sub-shell
p sub-shell Ar
Ionization energy

H
half-filled
p sub-shell
Li half-filled
1 Na
p sub-shell
erstand by the term atomic orbital? [1
show the shape of:
K
[1
Atomic number [1
2 2 6 2 6 8 2
electronic configuration 1s 2s 2p 3s 3p 3d 4s .
TheCheck
theSkill
Periodic‘drops’
Table2between
does elementgroups 2 and to?
X belong 13 occur because an electron is remove[1
mumThe higher
number in
of energy
electrons
1st ionisation than
energies dansub-shell.
s orbital
inofaseveral elementsand with hence is easier
consecutive atomicto remove.
numbers There is[1
are shown
2+
the The
ms aninion of type
graph ‘drops’
X .Thebetween
below. groups
letters are not 15 and
the symbols 16elements.
of the occurs because there are pa
2
ectronic
so confienergy
less gurationisfor this ion using
required to 1s notation.
remove one. This is due to the increased [1
a. Which of the elements A to I belong to Group I in the Periodic Table? Explain your answer.
ol for theThere
sub-shell is which
a largebegins
droptoatfillthe
afterend
the of
3d each
and 4speriod
are completely
becausefull.an electro[1
b.which
Which ofresults
the elements A to I could have the electronic configuration 1s2 2s2 2p6 3s2?Total =
in a large increase in shielding. Hence there is less attra
c.the nucleus.
Explain the rise in 1st ionisation energy between element E and element G.
ergies of several elements with consecutive atomic numbers are shown in the graph
For the s- and p-blocks the increase in nuclear charge across a per
notd.the
Estimate the of
symbols 1stthe
ionisation energy of element J.
elements.
on the outer shell (valence) electrons because the inner shielding onl
2000
First ionisation energy / kJ mol–1

1600

1200

1800

400

0
A B C D E F G H I J
Element

ents A to I belong to Group I in the Periodic Table? Explain your answer. [3

2 2 6 2
ents A to I could have the electronic configuration 1s 2s 2p 3s ? [1
1st ionisation energy between element E and element G. [4
nisation energy of element J. [2
 80 80
25 ( Br− Br)
Periodic Trends B −
79 81
C ( Br− Br) −
Skill Check 3
79
( Br− 81 +
The first ionisation of D
elements sodiumBr)
to argon is shown below. (1)
d) State and outline one modern use of mass
A Explain why the general trend from sodium to argon is upwards but why the value for
sulfur is less thanspectrometry.
that for phosphorus. (3)
(1) (Total 9 marks)
B Mark on the graph where the value for potassium would be.

C Explain3why The firstforionisation

the value of elements
the second ionisation of sodiumsodium tolarger than
is very much
argon
that of its first is shown below.
ionisation.
d?
First ionisation energy

(1)
(2)

Na Mg Al Si P S Cl Ar K

a) Explain why the general trend from sodium

Skill Check 4 to argon is upwards but why the value for
sulfur is less than that for phosphorus. (5)
(1) For each of the following pairs, state which element has the higher first ionisation energy
b) Mark
ks) and explain your answer: on the graph where the value for
A Mg and Al
potassium would be. (1)
c) Explain why the value for the second
he ionisation of sodium is very much larger
than that of its first ionisation. (2)
e B Mg and Ca (Total 8 marks)

(1)
(1)
C Ne and Na
(1)

ic 1)