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Inorganic chemistry
Chapters in this
section
8 Periodicity
9 Group 2, the alkaline
earth metals
10 Group 7(17), the
halogens
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Periodicity
Learning objectives:
State the location of the s-,
p-, and d-blocks of elements
in the Periodic Table.
Specification reference: 3.2.1
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
the table. You can use it to explain the similarities of certain elements and
the trends in their properties, in terms of their electronic arrangements.
3
4
5
6
7
metalloids
transition metals
halogens
0
noble (rare or inert) gases
alkali metals
The Periodic Table has been written in many forms including pyramids
and spirals. The one shown below (and at the end of the book) is one
common layout. Some areas of the Periodic Table are given names.
These are shown in Figure 1.
Lanthanides
lanthanides
Actinides
actinides
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.
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Periodicity
key
0
(18)
atomic symbol
1.0
hydrogen
4.0
name
(1)
(2)
6.9
9.0
10.8
12.0
14.0
16.0
19.0
20.2
beryllium
boron
carbon
nitrogen
oxygen
fluorine
neon
27.0
28.1
31.0
32.1
35.5
39.9
aluminium
silicon
phosphorus
sulfur
chlorine
argon
65.4
69.7
72.6
74.9
79.0
79.9
83.8
Li
lithium
Be
23.0
24.3
sodium
magnesium
39.1
Na
He
Mg
(3)
(4)
(5)
(6)
(7)
(8)
(9)
40.1
45.0
47.9
50.9
52.0
54.9
55.8
58.9
58.7
63.5
potassium
calcium
scandium
titanium
85.5
87.6
88.9
91.2
rubidium
strontium
yttrium
zirconium
132.9
137.3
138.9
caesium
barium
[223]
francium
11
19
Rb
37
Cs
55
Fr
87
12
Ca
20
Sr
Sc
21
Ti
22
Zr
Cr
Mn
Fe
Co
Ni
Cu
Zn
Al
13
Ga
Si
14
Ge
N
7
15
As
Cl
16
Se
17
Br
Ne
10
Ar
18
Kr
23
24
25
26
iron
cobalt
nickel
copper
29
30
zinc
gallium
germanium
arsenic
selenium
bromine
krypton
92.9
95.9
[98]
101.1
102.9
106.4
107.9
112.4
114.8
118.7
121.8
127.6
126.9
131.3
rhodium
palladium
silver
cadmium
indium
49
50
tin
antimony
tellurium
iodine
xenon
Nb
Mo
Tc
Ru
27
Rh
28
Pa
Cd
In
32
Sn
33
Sb
34
Te
35
36
Xe
42
43
44
178.5
180.9
183.8
186.2
190.2
192.2
195.1
197.0
200.6
204.4
207.2
209.0
[209]
[210]
[222]
lanthanum
hafnium
tantalum
tungsten
rhenium
osmium
iridium
platinum
78
gold
79
mercury
thallium
lead
bismuth
polonium
astatine
radon
[226]
[227]
[261]
[262]
[266]
[264]
[277]
[268]
[271]
[272]
radium
actinium
rutherfordium
bohrium
Ba
56
Ra
88
39
La*
57
Ac*
89
Hf
72
Rf
104
Ta
73
Db
74
Sg
dubnium seaborgium
105
106
Re
75
Bh
107
Os
76
Hs
108
45
Ir
77
Mt
109
46
Ag
31
41
38
40
helium
Pt
Ds
110
47
Au
48
Hg
80
Rg
111
Tl
81
Pb
82
51
Bi
83
52
Po
84
53
At
85
54
Rn
86
*the lanthanides (atomic numbers 5871) and the actinides (atomic numbers 90103) have been omitted
s-block
d-block
p-block
Areas of the table are labelled s-block, p-block, d-block, and f-block.
All the elements that have their highest energy electrons in s-orbitals
are in the s-block, for example, sodium, Na (1s2 2s2 2p6 3s1).
All the elements that have their highest energy electrons in
p-orbitals are called p-block, for example, carbon, C (1s2 2s2 2p2).
f-block
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lines to appear in the spectrum of light they give out. The letters s, p,
d, and f stand for words that were used first to describe the lines s for
sharp, p for principal, d for diffuse, and f for fine.
Groups
A group is a vertical column of elements. The elements in the
same group form a chemical family they have similar properties.
Elements in the same group have the same number of electrons in
the outer main level. The groups were traditionally numbered IVII
in Roman numerals plus zero for the noble gases, missing out the
transition elements. It is now common to number them in ordinary
numbers as 17 and 0 (or 18) and sometimes as 118 including the
transition metals.
Reactivity
In the s-block, elements (metals) get more reactive going down a
group. To the right (non-metals), elements tend to get more reactive
going up a group.
Transition elements are a block of rather unreactive metals. This is
where most of the useful metals are found.
Lanthanides are metals which are not often encountered. They all
tend to form +3 ions in their compounds and have broadly similar
reactivity.
Actinides are radioactive metals. Only thorium and uranium occur
naturally in the Earths crust in anything more than trace quantities.
Summary questions
1 From the elements, Br, Cl, Fe,
K, Cs, and Sb, pick out:
a two elements
i in the same period
ii in the same group
iii that are non-metals
b one element
i that is in the d-block
ii that is in the s-block.
2 From the elements Tl, Ge, Xe,
Sr, and W, pick out:
a a noble gas
b the element described by
Group 4, Period 4
c an s-block element
d a p-block element
e a d-block element.
Periods
Horizontal rows of elements in the Periodic Table are called periods.
The periods are numbered starting from Period 1, which contains
only hydrogen and helium. Period 2 contains the elements lithium to
neon, and so on. There are trends in physical properties and chemical
behaviour as you go across a period, see Topic 8.2.
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Learning objectives:
Describe the trends in melting
and boiling temperatures of
the elements in Period 3.
Explain these trends in terms
of bonding and structure.
Specification reference: 3.2.1
Silicon in Group 4 has four electrons in its outer shell with which
it forms four covalent bonds. The element has some metallic
properties and is classed as a semi-metal.
The elements in Groups 5, 6, and 7 (phosphorus, sulfur, and chlorine)
are non-metals. They either accept electrons to form ionic compounds,
or share their outer electrons to form covalent compounds.
Argon in Group 0 is a noble gas it has a full outer shell and is
unreactive.
Table 1 shows some trends across Period 3. Similar trends are found in
other periods.
1 2
3 4
5 6 7
Study tip
2
3 Na Mg
Al Si P S Cl Ar
4
5
6
7
4
silicon
[Ne] 3s2 3p2
semi-metal
macromolecular
(giant covalent)
giant metallic
Melting point,
Tm / K
371
922
933
1683
Boiling point,
Tb / K
1156
1380
2740
2628
5
phosphorus
6
sulfur
7
chlorine
0
argon
[Ne] 3s2 3p3 [Ne] 3s2 3p4 [Ne] 3s2 3p5 [Ne] 3s2 3p6
p-block
non-metals
molecular
S8
P4
317
392
(white)
(monoclinic)
553
(white)
718
Cl2
noble gas
atomic
Ar
172
84
238
87
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Hint
Synoptic link
Summary questions
3000
boiling point
melting point
2500
temperature / K
1 Whereabouts in a period do
you find the following? Choose
from left, right, middle.
a Elements that lose
electrons when forming
compounds
b Elements that accept
electrons when forming
compounds
2 In what group do you find an
element that exists as the
following?
a separate atoms
b a macromolecule
3 A and B are both elements.
Both conduct electricity
A well, B slightly. A melts at
a low temperature, B at a
much higher temperature.
Suggest the identity of A and B
and explain how their bonding
and structure account for
their properties.
Si
2000
Al
1500
Mg
1000
Na
P
S
500
0
11
12
13
14
15
16
Cl
17
Ar
18
atomic number
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Some key properties of atoms, such as size and ionisation energy, are
periodic, that is, there are similar trends as you go across each period
in the Periodic Table.
Atomic radii
These tell us about the sizes of atoms. You cannot measure the
radius of an isolated atom because there is no clear point at which
the electron cloud density around it drops to zero. Instead half the
distance between the centres of a pair of atoms is used, see Figure 1.
Learning objectives:
Describe the trends in atomic
radius and first ionisation
energy of the elements in
Period 3.
Explain these trends.
Specification reference: 3.2.1
Na
Mg
Al
Si
size of
atom
atomic
(covalent)
radius / nm
nuclear
charge
Cl
2,8,5
2,8,6
2,8,7
2,8,1
2,8,2
2,8,3
2,8,4
2,8,5
2,8,6
2,8,7
0.156
0.136
0.125
0.117
0.110
0.104
0.099
11+
12+
13+
14+
15+
16+
17+
Figure 3 The sizes and electronic structures of the elements sodium to chlorine
Hint
1 nm is 1 109 m
covalent
radius / nm
0.24
0.18
Li
0.12
Na
Period 2
Period 3
0.06
0.00
10
15
atomic number
20
Study tip
It is a common mistake to think
that atoms increase in size as you
cross a period. While the nuclei
have more protons (and neutrons)
the radius of the atom depends on
the size of the electron shells.
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Synoptic link
You learnt about ionisation energy
in Topic 1.6, Electron arrangements
and ionistion energy.
The first ionisation energies also have periodic patterns. These are
shown in Figure 4.
2500
He
Ne
2000
F
1500
Ar
1000
Cl
H
Be
Mg
B
500
S
Ca
Al
Li
Si
Na
5
10
K
15
20
atomic number
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Periodicity
11+
12+
13+
14+
15+
16+
17+
18+
[Ne]3s1
[Ne]3s2
[Ne]3s2 3p1
[Ne]3s2 3p2
[Ne]3s2 3p3
[Ne]3s2 3p4
[Ne]3s2 3p5
[Ne]3s2 3p6
Summary questions
1 What happens to the size of atoms as you go from left to right across a
period? Choose from increase, decrease, no change.
2 What happens to the first ionisation energy as you go from left to right
across a period? Choose from increase, decrease, no change.
3 What happens to the nuclear charge of the atoms as you go left to right
across a period?
4 Why do the noble gases have the highest first ionisation energy of all
the elements in their period?
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Hint
Ionisation energies are sometimes
called ionisation enthalpies.
This chapter revisits the trends in ionisation energies first dealt with
in Topic 1.6, in the context of periodicity. The graph of first ionisation
energy against atomic number across a period is not smooth. Figure 1
below shows the plot for Period 3.
1750
Learning objectives:
Group 0
Ar
1500
1250
Group 5
P
1000
500
Group 6
S
Group 2
Mg
750
Group 1
Na
Group 7
Cl
Group 4
Si
Group 3
Al
250
complete removal
1st IE
energy
3p
11
12
13
14
15
atomic number
16
17
18
3s
2p
2s
1s
Similar patterns occur in other periods. You can explain this if you
look at the electron arrangements of these elements.
1st IE
3p
complete removal
energy
0
10
3s
2p
2s
1s
aluminium 1s2 2s2 2p6 3s2 3p1
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Periodicity
1s
2s
2p
3s
3p
2s
2p
electrons in shell 2
electrons
in shell 3
0 1 2 3 4 5 6 7 8 9 10 11
total number of electrons removed
log IE
electrons
in shell 1
3s
3p
easier
to lose
electrons
in shell 1
electrons in shell 2
electrons
in shell 3
0 1 2 3 4 5 6 7 8 9 10 11 12 13
total number of electrons removed
Summary questions
1 Write the electron
arrangement in the form
1s2 for:
a beryllium
b boron.
2 If one electron is lost from
for the following atoms, from
what main level does it come?
a beryllium
b boron
3 Why is the first ionisation
energy of boron less than that
of beryllium?
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Practice questions
1
The following table gives the melting points of some elements in Period 3.
Element
Melting point / K
Na
371
Al
933
Si
1680
P
317
S
392
Trends in physical properties occur across all Periods in the Periodic Table.
This question is about trends in the Period 2 elements from lithium to nitrogen.
(a) Identify, from the Period 2 elements lithium to nitrogen, the element that has the
largest atomic radius.
(1 mark)
(b) (i) State the general trend in first ionisation energies for the Period 2 elements
lithium to nitrogen.
(1 mark)
(b) (ii) Identify the element that deviates from this general trend, from lithium to
nitrogen, and explain your answer.
(3 marks)
(c) Identify the Period 2 element that has the following successive ionisation energies.
Ionisation energy /
kJ mol1
First
Second
Third
Fourth
Fifth
Sixth
1090
2350
4610
6220
37 800
47 000
(1 mark)
AQA, 2012
(d) Draw a cross on the diagram to show the melting point of nitrogen.
5000
4500
4000
3500
3000
melting
2500
point/K
2000
1500
1000
500
0
lithium beryllium
boron
carbon nitrogen
(1 mark)
(e) Explain, in terms of structure and bonding, why the melting point of carbon is high.
(3 marks)
(1 mark)
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Chapter 8 Periodicity
3
(a) Use your knowledge of electron configuration and ionisation energies to answer this
question.
The following diagram shows the second ionisation energies of some Period 3 elements.
second ionisation
Mg
(i)
Al
Si
(1 mark)
(iii) Write an equation to show the process that occurs when the second ionisation
energy of aluminium is measured.
(1 mark)
(iv) Give one reason why the second ionisation energy of silicon is lower than the
second ionisation energy of aluminium.
(1 mark)
(b) Predict the element in Period 3 that has the highest second ionisation energy.
Give a reason for your answer.
(2 marks)
(c) The following table gives the successive ionisation energies of an element in Period 3.
Ionisation energy /
kJ mol1
First
Second
Third
Fourth
Fifth
Sixth
786
1580
3230
4360
16 100
19 800
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Learning objectives
Explain the changes in the
atomic radius of the Group 2
elements from Mg to Ba.
Explain the changes in the first
ionisation energy of the Group 2
elements from Mg to Ba.
Explain the changes in the
melting point of the Group 2
elements from Mg to Ba.
State the trend in reactivity
of the group.
State the trend in solubilities
of a) the hydroxides b) the
sulfates.
Specification reference: 3.2.2
Electron arrangement
The elements all have two electrons in an outer s-orbital. This s-orbital
becomes further away from the nucleus going down the group.
Melting points
Synoptic link
Look back at Topic 3.3, Metallic
bonding for more on the giant
metallic structure.
Group 2 elements are metals with high melting points, typical of a giant
metallic structure. Going down the group, the electrons in the sea
of delocalised electrons are further away from the positive nuclei. As
a result, the strength of the metallic bonds decreases going down the
group. For this reason the melting points of Group 2 elements decrease
slightly going down the group, starting with calcium.
Magnesium, with the lowest melting point, does not fit this trend
but there is no simple explanation for this anomaly.
Ionisation energies
In all their reactions, atoms of elements in Group 2 lose their two
outer electrons to form ions with two positive charges.
Hint
Remember the shorthand for
writing electron arrangements
using the previous inert gas.
So [Ne]3s2 is shorthand for
1s2,2s2,2p6,3s2.
M(g) M(g)2+ + 2e
So, an amount of energy equal to the sum of the first and the second
ionisation energies is needed for complete ionisation.
M(g) M+(g) + e
plus
Both the first ionisation energy and the second ionisation energy decrease
going down the group it takes less energy to remove the electrons as
they become further and further away from the positive nucleus. The
nucleus is more effectively shielded by more inner shells of electrons.
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Atomic
Electron
Metallic
number Z arrangement radius / nm
[Ne]3s2
[Ar]4s2
[Kr]5s2
[Xe]6s2
magnesium, Mg
calcium, Ca
strontium, Sr
barium, Ba
12
20
38
56
0.160
0.197
0.215
0.224
1380
1757
1657
1913
1.74
1.54
2.60
3.51
In all their reactions, the metals get more reactive going down the group.
Lime kilns
Disused lime kilns can be found in many areas where there is limestone rock.
Limestone is mainly calcium carbonate, CaCO3, and it was heated in kilns
fired by wood or coal to produce quicklime (calcium oxide, CaO) which was
used to make building mortar, to treat acidic soils, and in making glass.
In the kiln, heat decomposes the limestone:
CaCO3(s) CaO(s) + CO2(g)
A typical kiln contained around 25 tonnes of limestone.
1
2 Give two reasons why lime kilns were significant emitters of carbon dioxide.
3 The limestone was broken into fist-sized lumps before firing. Suggest why.
In practice limestone is unlikely to be found 100% pure. One contaminant is
silicon dioxide (sand), which is unaffected by heat. Imagine limestone that
contains 15% sand, so 100 tonnes of limestone would contain 85 tonnes of
calcium carbonate.
4 Rework the calculation above to calculate how much lime would
actually be produced.
Both lime (calcium oxide, CaO) and slaked lime (calcium hydroxide, Ca(OH)2)
may be used to neutralise acids in soil.
The equations for their reactions with hydrochloric acid (for simplicity) are
given below.
CaO(s) + 2HCl(aq) CaCl2(aq) + H2O(l)
Ca(OH)2(s) + 2HCl(aq) CaCl2(aq) + 2H2O(l)
5 How many moles of a lime and b quicklime are needed to neutralise
2 mol HCl?
6 How many grams of a lime and b slaked lime are needed to neutralise
2 mol HCl?
7 What implications does this have for the farmer or gardener?
8 Suggest other factors to be considered when deciding which
compound to use.
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Hint
Remember lower pH means more
acidic.
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Hint
Hint
The symbol aq is used to represent
an unspecified amount of water.
Sulfates
The solubility trend in the sulfates is exactly the opposite they become
less soluble going down the group. So, barium sulfate is virtually
insoluble. This means that it can be taken by mouth as a barium meal
to outline the gut in medical X-rays. (The heavy barium atom is very
good at absorbing X-rays.) This test is safe, despite the fact that barium
compounds are highly toxic, because barium sulfate is so insoluble.
The insolubility of barium sulfate is also used in a simple test for sulfate
ions in solution. The solution is first acidified with nitric or hydrochloric
acid. Then barium chloride solution is added to the solution under test
and if a sulfate is present a white precipitate of barium sulfate is formed.
Ba2+(aq) + SO42(aq) BaSO4(s)
The addition of acid removes carbonate ions as carbon dioxide.
(Barium carbonate is also a white insoluble solid, which would be
indistinguishable from barium sulfate).
Summary questions
1 a What is the oxidation number of all Group 2
elements in their compounds?
b Explain your answer.
2 Why does it become easier to form +2 ions going
down Group 2?
3 Explain why this is a redox reaction.
Ca + Cl2 CaCl2
4 Write the equation for the reaction of calcium with
water. Include the oxidation state of each element.
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Practice questions
1
State and explain the trend in melting point of the Group 2 elements Ca to Ba.
(3 marks)
AQA, 2006
State the trends in solubility of the hydroxides and of the sulfates of the Group 2
elements Mg to Ba.
Describe a chemical test you could perform to distinguish between separate aqueous
solutions of sodium sulfate and sodium nitrate. State the observation you would make
with each solution. Write an equation for any reaction which occurs.
(6 marks)
(a) For the elements Mg to Ba, state how the solubilities of the hydroxides and the
solubilities of the sulfates change down Group 2.
(b) Describe a test to show the presence of sulfate ions in an aqueous solution. Give the
results of this test when performed on separate aqueous solutions of magnesium
chloride and magnesium sulfate. Write equations for any reactions occurring.
(c) State the trend in the reactivity of the Group 2 elements Mg to Ba with water.
Write an ionic equation with state symbols to show the reaction of barium with an
excess of water.
(9 marks)
Group 2 metals and their compounds are used commercially in a variety of processes
and applications.
(a) State a use of magnesium hydroxide in medicine.
(1 mark)
(b) Calcium carbonate is an insoluble solid that can be used in a reaction to
lower the acidity of the water in a lake.
Explain why the rate of this reaction decreases when the temperature of the
water in the lake falls.
(3 marks)
(c) Strontium metal is used in the manufacture of alloys.
(i) Explain why strontium has a higher melting point than barium.
(2 marks)
(ii) Write an equation for the reaction of strontium with water.
(1 mark)
(d) Magnesium can be used in the extraction of titanium.
(i) Write an equation for the reaction of magnesium with titanium(IV) chloride.
(1 mark)
(ii) The excess of magnesium used in this extraction can be removed by
reacting it with dilute sulfuric acid to form magnesium sulfate.
Use your knowledge of Group 2 sulfates to explain why the magnesium sulfate
formed is easy to separate from the titanium.
(1 mark)
AQA, 2006
AQA, 2005
AQA, 2010
increases
(1 mark)
increases
(1 mark)
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increases
(1 mark)
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The following diagram shows the first ionisation energies of some Period 3 elements.
1200
1000
800
600
1400
400
Na Mg
Al
Si
Cl
(a) Draw a cross on the diagram to show the first ionisation energy of aluminium.
(1 mark)
(b) Write an equation to show the process that occurs when the first ionisation
energy of aluminium is measured.
(2 marks)
(c) State which of the first, second or third ionisations of aluminium would
produce an ion with the electron configuration 1s2 2s2 2p6 3s1
(1 mark)
(d) Explain why the value of the first ionisation energy of sulfur is less than
the value of the first ionisation energy of phosphorus.
(2 marks)
(e) Identify the element in Period 2 that has the highest first ionisation energy and give
its electron configuration.
(2 marks)
(f) State the trend in first ionisation energies in Group 2 from beryllium to barium.
Explain your answer in terms of a suitable model of atomic structure.
(3 marks)
AQA, 2010
159
835181_AQA_AS_Chemistry SB_Ch09.indd 159
25/03/2015 08:22