3.1.

1 The Periodic Table

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Structure of the Periodic Table
 The periodic table is a list of all known elements arranged in order
of increasing atomic number, from 1 to 118.
 In addition to this, the elements are arranged in such a way that atoms with
the same number of shells are placed together, and atoms with similar
electronic configurations in the outer shell are also placed together. This is
achieved as follows:
o The elements are arranged in rows and columns.

o Elements with one shell are placed in the first row (i.e. H and He)

o Elements with two shells are placed in the second row (Li to Ne) and

so on.
 A row of elements thus arranged is called a period. The period number, n, is
the outer energy level that is occupied by electrons.
 In addition, the elements are aligned vertically (in columns) with other
elements in different rows, if they share a similar outer-shell electronic
configuration
o The outer electrons are known as the valence electrons.

 A column of elements thus arranged is called a group

 Since the electronic configurations of H and He are unusual, they do not fit
comfortably into any group. They are thus allocated a group based on
similarities in physical and chemical properties with other members of the
group
 He is placed in group 0 on this basis, but hydrogen does not behave like any
other element and so is placed in a group of its own
 The blocks of the periodic table
 All elements belong to one of four main blocks: the s-block, the p-block, the
d-block and the f-block
o The s-block elements are all those with only s electrons in the
outer shell
o The p-block elements are all those with at least one p-electron in
the outer shell
o The d-block elements are all those with at least one d-electron and
at least one s-electron but no f or p electrons in the outer shell (up
to 5d)
o The f-block elements are all those with at least one f-electron and
at least one s-electron but no d or p electrons in the outer shell
 The physical and chemical properties of elements in the periodic table show
clear patterns related to the position of each element in the table
o Elements in the same group show similar properties, and properties
change gradually as you go across a period
 As atomic number increases, the properties of the elements show trends
which repeat themselves in each period of the periodic table
o These trends are known as periodic trends and the study of these
trends in known as periodicity
Deducing Electron Configurations
 The electron configuration of any element can be deduced from its position in
the periodic table
 It is like an ‘address’ that tells you exactly where an element is found
 Using the element germanium as an example to illustrate how it works:
 Deducing the electron configuration of germanium
 Germanium is in p block, in group 4 (using the simplifi numbering system)
and the second element across in period 4
 Group 4 tells you there are four valence electrons and period 4 tells you
the valence electrons are in the fourth shell
 The second position in p block tell you that two electrons are in the p
subshell
 Similarly, you can deduce the position of an element in the periodic table from
its electron configuration:

Deducing information from the electron configuration of chlorine

 
 Test your understanding in the following example:
Worked Example
Element Z is in period 4 and group 5 of the periodic table. Which statement is
correct?
   A.  Z has 5 occupied energy levels.
   B.  Z can form ions with 3– charge.
   C.  Z is a transition element.
   D.  Z has 4 valence electrons.
Answer:


o The correct option is B. A group 5 element could form a 3- ion

o It cannot be A because 5 occupied energy levels would place it in

period 5
o Transition elements would not be found in group 5, so C is also
incorrect
o 4 valence electrons would match an element in group 4, so D must be
wrong
3.1.2 Periodic Trends: Physical - Atomic & Ionic Radius
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Atomic & Ionic Radius
Atomic radius
 The atomic radius of an element is a measure of the size of an atom
 It is the distance between the nucleus of an atom and the outermost electron
shell
 It can be quite hard to determine exactly where the boundary of an atom lies,
so a variety of approches are taken such as half the mean distance between
two adjacent atoms
 This will vary depending on the type of structure and bonding, but it gives a
comparative value for atoms

The atomic radius of an atom is the typical distance between the nucleus and
the outermost electron shell
 Atomic radii show predictable patterns across the periodic table
o They generally decrease across each period

o They generally increase down each group

 These trends can be explained by the electron shell theory

o Atomic radii decrease as you move across a period as the atomic
number increases (increased positive nuclear charge) but at the same
time extra electrons are added to the same principal quantum shell
o The larger the nuclear charge, the greater the pull of the nuclei on the
electrons which results in smaller atoms
o Atomic radii increase moving down a group as there is an increased
number of shells going down the group
o The electrons in the inner shells repel the electrons in the outermost
shells, shielding them from the positive nuclear charge
o This weakens the pull of the nuclei on the electrons resulting in larger
atoms
 Trends in the atomic radii across a period and down a group
 The diagram shows that the atomic radius increases sharply between
the noble gas at the end of each period and the alkali metal at the beginning
of the next period
 This is because the alkali metals at the beginning of the next period
have one extra principal quantum shell
o This increases shielding of the outermost electrons and therefore
increases the atomic radius

Ionic radius
 The ionic radius of an element is a measure of the size of an ion
 Ionic radii show predictable patterns
o The trend down a group is the same as atomic radius – it increases as
the number of shells increases
 o The trend across a period is not so straightforward as it depends on
whether it is positive or negative ions being considered
o Ionic radii increase with increasing negative charge

o Ionic radii decrease with increasing positive charge

 These trends can also be explained by the electron shell theory

o Ions with negative charges are formed by atoms accepting extra
electrons while the nuclear charge remains the same
o The extra electrons experience repulsion with the other valence
electrons which increases the ionic radius
o The greater the negative charge, the larger the ionic radius

o Positively charged ions are formed by atoms losing electrons

o The nuclear charge remains the same but there are now fewer

electrons which undergo a greater electrostatic force of
attraction towards the nucleus which decreases the ionic radius
o The greater the positive charge, the smaller the ionic radius
 Trends in the ionic radii across a period and down a group
Worked Example
Which option shows atoms in order of decreasing atomic radius?
A. N > C > Be > Mg
B. Mg > N > C > Be
C. Be > C > N > Mg
D. Mg > Be > C > N
Answer:
Option D is the correct answer
 

o First, you need to identify that Be, C and N are all in period 2, but Mg is
in period 3, so Mg will have the biggest radius.
o Secondly, atomic radius decreases across the period so Be, C and N
decrease in that order as they belong to groups 2, 14 and 15,
respectively
3.1.3 Periodic Trends: Physical - Ionization Energy
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First Ionisation Energy
 The ionisation energy (IE) of an element is the amount of energy required to
remove one mole of electrons from one mole of atoms of an element in the
gaseous state to form one mole of gaseous ions
 Ionisation energies are measured under standard conditions which are 298
K and 100 kPa
 The units of IE are kilojoules per mole (kJ mol-1)
 The first ionisation energy is the energy required to remove the one mole of
electrons from one mole the gaseous atoms
o E.g. the first ionisation energy of calcium:

Ca(g) → Ca+ (g) + e–            1st   ∆H I.E. = +590 kJ mol-1

Ionisation Energies: Trends
 Ionisation energies show periodicity
 As could be expected from their electronic configuration, the group I metals
show low IE whereas the noble gases have very high IEs
 The first ionisation energy increases across a period and decreases down
a group and is caused by four factors that influence the ionisation energy:
o Size of the nuclear charge: the nuclear charge increases with
increasing atomic number, which means that there are
greater attractive forces between the nucleus and outer electrons, so
more energy is required to overcome these attractive forces when
removing an electron
o Distance of outer electrons from the nucleus: electrons in shells
that are further away from the nucleus are less attracted to the nucleus
so the further the outer electron shell is from the nucleus, the lower the
ionisation energy
o Shielding effect of inner electrons: the shielding effect is when the
electrons in full inner shells repel electrons in outer shells preventing
them to feel the full nuclear charge so the greater the shielding of
outer electrons by inner electron shells, the lower the ionisation energy
 o Spin-pair repulsion: paired electrons in the same atomic orbital in a
subshell repel each other more than electrons in different atomic
orbitals; this makes it easier to remove an electron (which is why the
first ionization energy is always the lowest)

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

Ionisation energy across a period

 The ionisation energy across a period increases due to the following factors:
o Across a period the nuclear charge increases

o The distance between the nucleus and outer electron remains

reasonably constant
o The shielding by inner shell electrons remains the same

 There is a rapid decrease in ionisation energy between the last element in

one period and the first element in the next period caused by:
o The increased distance between the nucleus and the outer electrons

o The increased shielding by inner electrons

o These two factors outweigh the increased nuclear charge

 There is a slight decrease in 1st I.E. between beryllium and boron as the

fifth electron in boron is in the 2p subshell which is further away from the
nucleus than the 2s subshell of beryllium
 o Beryllium has a first ionisation energy of 900 kJ mol-1 as its electron
configuration is 1s2 2s2
o Boron has a first ionisation energy of 801 kJ mol-1 as its electron
configuration is 1s2 2s2 2p1
 There is a slight decrease in 1st I.E. between nitrogen and oxygen due
to spin-pair repulsion in the 2p subshell of oxygen
o Nitrogen has a first ionisation energy of 1402 kJ mol-1 as its electron
configuration is 1s2 2s2 2p3
o Oxygen has a first ionisation energy of 1314 kJ mol-1 as its electron
configuration is 1s2 2s2 2p4


Ionisation energy down a group

 Although going down a group the nuclear charge increases, the ionisation
energy down a group decreases and it is due to the following factors:
o The distance between the nucleus and outer electron increases

o The shielding by inner shell electrons increases

o The effective nuclear charge is decreasing as shielding increases

Ionisation Energy Trends across a Period & going down a Group Table
Successive ionisation energies of an element
 The successive ionisation energies of an element increase as removing an
electron from a positive ion is more difficult than from a neutral atom
 As more electrons are removed the attractive forces increase due
to decreasing shielding and an increase in the proton to electron ratio
 The increase in ionisation energy, however, is not constant and is dependent
on the atom’s electronic configuration
 Taking calcium as an example:
Ionisation Energies of Calcium Table
 The values become very large and difficult to represent meaningfully, so it is
more convenient to show the logarithm of the ionisation energies
 This helps us to see significant jumps in I.E.

Successive ionisation energies for the element calcium

 The first electron removed has a low ionisation energy as it is easily removed
from the atom due to the spin-pair repulsion of the electrons in the 4s orbital
 The second electron is a little more difficult to remove than the first electron
as you are removing an electron from a positively charged ion
 The third electron is much more difficult to remove than the second one
corresponding to the fact that the third electron is in a principal
quantum shell which is closer to the nucleus (3p)
 The graph shows there is a large increase in successive ionisation energy as
the electrons are being removed from an increasingly positive ion
  The big jumps on the graph show the change of shell and the small jumps are
the change of subshell
Exam Tip
Be careful with how you interpret successive ionisation energy graphs as it is
common for students to read them the wrong way around and count outer electrons
from right to left instead of left to right so they get the jumps in the wrong place. This
happens particularly when you are given only a partial successive ionisation energy
graph and have to deduce which group the element comes from.
It’s a good idea if you see an ionisation energy graph in an exam question to label
the shells and subshells so you are less likely to make this mistake!
3.1.4 Periodic Trends: Physical - Electron Affinity
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Electron Affinity
 When atoms gain electrons they become negative ions or anions
 Electron affinity (EA) can be thought of as the opposite process of ionisation
energy and is defined as
o The amount of energy released when one mole of electrons is gained
by one mole of atoms of an element in the gaseous state to form one
mole of gaseous ions
 Electron affinities are measured under standard conditions which are 298 K
and 100 kPa
 The units of EA are kilojoules per mole (kJ mol-1)
 The first electron affinity is always exothermic
o E.g. the first electron affinity of chlorine is:

Cl (g) + e– → Cl– (g)                 ∆H = – 349 kJ mol-1

 However, the second electron affinity can be an endothermic process
O– (g) + e– → O2- (g)              ∆H = + 753 kJ mol-1
 This is due to the fact that you are overcoming repulsion between the electron
and a negative ion, so energy is required making the process endothermic
overall

Trends in electron affinity

 Electron affinities across a period
 Electron affinities show periodicity
 The pattern is very similar to ionisation energies, except that it is inverted and
the minimum points are displaced one element to the right
 As might be expected, the most exothermic electron affinities are for group 17
elements which also have the highest electronegativities
 The strongest pull on electrons correlates with the greater amount of energy
released when negative ions are formed
 Noble gases do not form negative ions, so they don’t appear in this chart
 The electron affinities reach a peak for group 2 and group 5 elements

Electron affinities down a group

 Electron affinities generally decrease down a group
 As the atoms become larger the attraction for an additional electron is less,
since the effective nuclear charge is reduced due to increased shielding
 Electron affinity become less exothermic going down the group
 An exception to this is fluorine whose electron affinity is smaller than
expected
  This is because fluorine is such a small atom and an additional electron in the
2p subshell experiences considerable repulsion with the other valence
electrons
3.1.5 Periodic Trends: Physical - Electronegativity
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Electronegativity: Definition
 Electronegativity is the ability of an atom to attract a pair of electrons
towards itself in a covalent bond
 This phenomenon arises from the positive nucleus’s ability to attract
the negatively charged electrons, in the outer shells, towards itself
 The Pauling scale is used to assign a value of electronegativity for each
atom

First three rows of the periodic table showing electronegativity values

 Fluorine is the most electronegative atom on the Periodic Table, with a value
of 4.0 on the Pauling Scale
 It is best at attracting electron density towards itself when covalently bonded
to another atom
 Electron distribution in the C-F bond of fluoromethane
Electronegativity: Affecting Factors
Nuclear charge
 Attraction exists between the positively charged protons in the nucleus and
negatively charged electrons found in the energy levels of an atom
 An increase in the number of protons leads to
an increase in nuclear attraction for the electrons in the outer shells
 Therefore, an increased nuclear charge results in an increased
electronegativity

As the nuclear charge increases, the electronegativity of an element increases

as well

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

As the atomic radius increases, the nucleus has less of an attraction for the
bonding electrons causing atom A to have a higher electronegativity than
atom B
Electronegativity: Trends
 Electronegativity varies across periods and down the groups of the periodic
table

Down a group
 There is a decrease in electronegativity going down the group
 The nuclear charge increases as more protons are being added to the
nucleus
 However, each element has an extra filled electron shell, which
increases shielding
 The addition of the extra shells increases the distance between the nucleus
and the outer electrons resulting in larger atomic radii
 Overall, there is decrease in attraction between the nucleus and outer
bonding electrons
 We say the effective nuclear charge has decreased down the group
 Electronegativity decreases going down the groups of the periodic table

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

Electronegativity increases going across the periods of the periodic table

Trends down a Group & across a Period Table
Exam Tip
Make sure you learn the definition of electronegativity and can distinguish it
from electron affinity as the two are often confused. Electronegativity is about
chemical character and only applies to considerations of covalent bonds
whereas electron affinity is a thermodynamic value that is measurable and applies
to the formation of negative ions.
You may come across something called electropositivity – this is a term used to
describe the character of elements to form positive ions and is useful when talking
about metal atoms and metal ions
3.1.6 Periodic Trends: Chemical
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Metallic & Non-metallic
 Periodic trends can also be seen in the typical properties of metals and non-
metals which are summarised below:
 The typical properties of metals and non-metals
 The typically properties of metals and non-metals can be explained by
reference to their trends in atomic radius, ionic radius, ionisation energy,
electron affinity and electronegativity
 The low ionisation energies and low electronegativities of metals can
account for the ability of their valence electrons to move away from the
nucleus
o This is known as ‘delocalisation‘ of the electrons

 These properties increase from left to right as you transition from metal to
metalloid to non-metal
 The high electronegativity and electron affinity of non-metals can be
related to their tendency to share electrons and form covalent bonds, either
with themselves or other non-metal elements
 The similarities in electronegativities of the diagonal band
of metalloids which divides the metals from the non-metals explains the
behaviour of metalloids
 
Test yourself on the trends in the periodic table:
Worked Example
Which increase across a period from left to right?
Answer:
The correct option is D


o Across a period atomic radius decreases, electronegativity and

ionisation energy increase and ionic radius increases then decreases
3.1.7 Periodic Trends: Oxides across a Period
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Oxides
Oxides across a period
 The acid-base character of the oxides provides evidence of chemical trends
in the periodic table
 The broad trend is that oxides change
from basic through amphoteric to acidic across a period
 Aluminium oxide is amphoteric which means that it can act both as a base
(and react with an acid such as HCl) and an acid (and react with a base such
as NaOH)
Acidic & Basic Nature of the Period 3 Oxides
 The acidic and basic nature of the Period 3 elements can be explained by
looking at their structure, bonding and the Period 3
elements’ electronegativity
Structure, Bonding & Electronegativity of the Period 3 Elements Table

 The difference in electronegativity between oxygen and Na, Mg and Al is the

largest
 Electrons will therefore be transferred to oxygen when forming oxides giving
the oxide an ionic bond
 The oxides of Si, P and S will share the electrons with the oxygen to
form covalently bonded oxides
 The oxides of Na and Mg which show purely ionic
bonding produce alkaline solutions with water as their oxide ions (O2-)
become hydroxide ions (OH–):
O2-(aq) + H2O(l) → 2OH–(aq)
 The oxides of P and S which show purely covalent
bonding produce acidic solutions with water because when these oxides
react with water, they form an acid which donates H+ ions to water
o Eg. SO3 reacts with water as follows:

SO3(g) + H2O(l) → H2SO4(aq)



o The H2SO4 is an acid which will donate an H+ to water:

H2SO4(aq) + H2O(l) → H3O+ (aq) + HSO4–(aq)

Exam Tip
Only examples of general trends across periods and groups are required, but you
should be able to link trends in ionization energy, electron affinity and
electronegativity with trends in chemical character such as the nature of the oxides
and metallic/ non-metallic behaviour.
Oxides reacting with Water
 The pH changes for the reactions of the oxides with water can be explained
by reference to the following equations
Reaction of Oxides with Water

 The pattern here is that:

o The metallic oxides form hydroxides when they react with water

o The non-metallic oxides form oxoacids when they react with water
Exam Tip
You should learn how to construct these equations exactly as they are specifically
mentioned in the syllabus
Making Predictions
 The position of an element in the periodic table can be used to predict and
explain its metallic and non-metallic behaviour
 This is illustrated by the bonding of the oxides
  Metal and non-metal elements generally form ionic compounds so the
elements Na to Al have giant ionic structures
 The oxides become more ionic as you go down the group as
the electronegativity decreases
 The oxides become less ionic as you go across a period as
the electronegativity increases
 The oxides of non-metals such as S, N and P form molecular covalent
compounds
 
 Sometimes you may be asked to make predictions about oxides that are not
specifically mentioned in the syllabus but you should be able deduce their
properties if you understand the patterns outlined above, as the following
example shows:
Worked Example
Which of these oxides produces the solution with the highest pH when added to
water ?
   A.  CO2
   B.  SO3
   C.  CaO
   D.  Na2O
Answer:
The correct option is D.
CO2 and SO3 will produce a pH below 7 as they are non-metal oxides. CaO and
Na2O will produce a pH above 7 as they are metal oxides; however the pH is
decreasing as you go across a period, so Na2O will have a higher pH than CaO
3.1.8 Periodic Trends: Group 1 - The Alkali Metals
Alkali Metals
The group 1 metals
 The group 1 metals are called the alkali metals because they form alkaline
solutions with high pH values when reacted with water
 Group 1 metals are lithium, sodium, potassium, rubidium, caesium and
francium
 They all end in the electron configuration ns1

Physical properties of the group 1 metals

 The group 1 metals:
 o Are soft and easy to cut, getting softer and denser as you move down
the group
o Have shiny silvery surfaces when freshly cut

o Conduct heat and electricity

o They all have low melting points and low densities and the melting

point decreases going down the group as the atomic radius increases
and the metallic bonding gets weaker

The alkali metals are located on the left of the periodic table in the first column
of the s block

Chemical properties of the Group 1 metals

 They react readily with oxygen and water vapour in air so they are usually
kept under oil to stop them from reacting
 Group 1 metals will react similarly with water, reacting vigorously to produce
an alkaline metal hydroxide solution and hydrogen gas
The Reactions of Group 1 Metals and Water
 
 Test yourself on this example question:
Worked Example
What would you see when sodium is added to water?
I.   a gas is given off
II.  the temperature of the water increases
III.  a clear, colourless solution is formed
A. I and II only
B. I and III only
C. II and III only
D. I, II and III
Answer:
The correct option is D.


o Bubbles of hydrogen gas are given off. The sodium melts, so that tells
you it is an exothermic reaction and the product, sodium hydroxide, is
very soluble so a clear, colourless solution would be formed.
Alkali metals with halogens
 All the alkali metals react vigorously with the halogens in group 17
 The reaction results in an alkali metal halide salt
2Na (s) + Cl2 (g) → 2NaCl (s)
 The reaction becomes increasingly vigorous going down group 1 because
o The atoms of each element get larger going down the group

o This means that the ns1 electron gets further away from the nucleus

and is shielded by more electron shells.
o The further an electron is from the positive nucleus, the easier it can be
lost in reactions
 
Can you apply what you have just learned? Check out the following example
question:
Worked Example
Which pair of elements has the most vigorous reaction?
   A.  Cs and I
   B.  Li and Cl
   C.  Cs and F
   D.  Li and F
Answer:
The correct option is C.
You need to choose the lowest element in group 1 and the highest element in group
17 to predict the most vigorous reaction as reactivity increases going down group 1,
but decreases going down group 17
3.1.9 Periodic Trends: Group 17 - The Halogens
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Halogens
The halogens
 These are the group 17 non-metals that are poisonous and include fluorine,
chlorine, bromine, iodine and astatine
 Halogens are diatomic, meaning they form molecules of two atoms
 All halogens have seven electrons in their outer shell
 They form halide ions by gaining one more electron to complete their outer
shells
 Colours and States at Room Temperature

Trends in physical properties of the halogens

Melting point
 The density and melting and boiling points of the halogens increase as you
go down the group

Explaining the trend in reactivity in Group VII

 Reactivity of group 17 non-metals decreases as you go down the group
 The halogens electron configurations all end in ns2np5
 Each outer shell contains seven electrons and when they react, they will need
to gain one outer electron to get a full outer shell of electrons
  Going down the group, the electron affinity decreases and the atomic
radius increases
 As you go down group 17, the number of shells of
electrons increases so shielding also increases
 This means that the outer electrons are further from the nucleus so there
are weaker electrostatic forces of attraction that attract the extra electron
needed
 The electron is attracted less readily, so the lower down the element is in
Group 17 the less reactive it is
Reaction of the halogens with halide ions in displacement reactions
 A halogen displacement occurs when a more reactive halogen displaces
a less reactive halogen from an aqueous solution of its halide
 The reactivity of group 17 non-metals increases as you move up the group
 Out of the 3 halogens, chlorine, bromine and iodine, chlorine is the most
reactive and iodine is the least reactive
Aqueous Solution Colour of Halogens

Halogen displacement reactions

Chlorine and bromine
 If you add chlorine solution to colourless potassium bromide solution, the
solution becomes orange as bromine is formed
 Chlorine is above bromine in group 17 so it is more reactive
 Chlorine will therefore displace bromine from an aqueous solution of a metal
bromide
          2KBr (aq)       +    Cl2 (aq)  →     2KCl (aq)     +       Br2(aq)
potassium bromide + chlorine → potassium chloride + bromine
Bromine and iodine
 Bromine is above iodine in group 17 so it is more reactive
 Bromine will therefore displace iodine from an aqueous solution of a metal
iodide
    Br2 (l) +      2NaI (aq)    →    2NaBr (aq)     +    I2 (aq)
bromine +  sodium Iodide → sodium bromide + iodine
 
Test yourself on halogen displacements:
Worked Example
Which of the statements below are correct?
I.   potassium chloride solution will react with fluorine to form chlorine.
II.  sodium chloride solution will react with iodine to form chlorine.
III. lithium iodide solution will react with bromine to form iodine.
  A.  I and II only
  B.  I and III only
  C.  II and III only
  D.  I, II and III
Answer:
The correct option is B.


o Fluorine will displace chlorine as it is higher up in the group and

bromine will displace iodine for the same reason.
o Iodine is below chlorine so cannot displace chlorine from sodium
chloride