CAPE Chemistry Unit 1

Study Notes 2
Topics:

31: Atomic and Physical Properties of Period 3

32: Physical Properties of Group 2, 4, 7 Elements
33: Halogens in solution
34: Transition elements
35: Qualitative Analysis

1
30: Chemistry of the Elements

1.3 Variation in oxidation number of Period 3 Oxides and Chlorides

1.4 Describe the reaction of the Oxides and Chlorides with water

(A) Reaction of Oxides with Water

2
Table showing the reaction of oxides with water.

3
(B) Reaction of Chlorides with water

Table 3 showing the reaction of chlorides with water.

4
Predict the type of bonding in the chlorides.

5
1.5 Trend in the acid/base behaviour of the oxides and hydroxides

1.6 Chemical bonding in oxides and hydroxides

Oxides

6
Hydroxides

Group II Elements

2.1 Explain the variation in properties of group II elements in terms of structure and bonding.

Members of the group being studied:

Beryllium Be
Magnesium Mg
Calcium Ca
Strontium Sr
Barium Ba

Group II elements are metals and undergo metallic bonding. Many of the properties of group
II elements are due to the presence of metallic bonds. These includes: electrical conductivity,
thermal conductivity, malleability, ductility, melting and boiling points.

Reactivity

As you go down the group reactivity increases with increasing atomic number. The further
away the outer shell is from the nucleus the easier it is for the element to react. For the
element to react it has to lose its 2 valence electrons found on the s orbital. When the atomic
radius increases the attraction between the nucleus and the electron decreases therefore the

7
ionization energy needed is less so the electron is removed quickly and the element will
react. This means that elements with a small atomic radius will have higher ionization energy
and so will be less reactive. Shielding effect is also a consideration when looking at the
increase in reactivity down the group. With each successive element there is greater
shielding of the outer electrons by the inner electron shells.

Ionization Energies
The 1st ionization energy of an element involves removing an electron from the outer most
orbital. Group II elements have very low ionization energies. As the atomic radius increases
the ionization energy decreases, because the electrons being ionized are further away from
the nucleus and there is more shielding.

Melting and Boiling Points

Larger atoms tend to have smaller first ionization energies because the valence electron
concerned is further from the nucleus. Larger positive ions have lower charge density, so
they have a smaller attraction for the delocalize electrons within the metallic structure. As a
result, melting point within a group usually decreases with increasing atomic number.

2.2 The reactions of Group II elements with Oxygen, Water and Dilute Acids

With oxygen

The Group II metal oxides are all white solids.

With water
All these metals reduce water to hydrogen.
Magnesium reacts readily with steam to form MgO and H2. All of the other metals react
readily with water to form a white suspension of the hydroxide (which is sparingly soluble)
and hydrogen.

8
With dilute acid
All of the reactions are similar. They displace hydrogen from dilute acids as they are all
above hydrogen in the reactivity series.

2.3 The variation in the solubilities of the sulphates of Group II elements

Solubility decreases down the Group.

The lattice enthalpies of the three sulphates are quite similar because the sulphate ion is a
very large ion, the changing size of the metal ion has little effect on it.

On the other hand, the enthalpies of hydration become significantly smaller as the metal ion
size increases (larger negative value). The sum of the enthalpy of hydration and the lattice
energy therefore becomes correspondingly more endothermic (less favourable to solution)
with increasing atomic number. (If the value is exothermic it means that the system that
results is energetically stable. As one proceeds down the Group the enthalpy becomes less
exothermic or more endothermic, so it becomes increasingly more difficult for the sulphate to
dissolve). At the bottom of the Group, although the endothermic enthalpy change of
hydration is lower, the enthalpy change of hydration is not enough to give such a high
solubility.

9
2.4: The Stability of the Carbonates and Nitrates to Heat

The Group II metals form carbonates of the formula MCO3 and the metal nitrates of formula
M(N03)2.
When heated the carbonates decompose to form the metal oxide and carbon dioxide.

When heated the nitrates decompose to form the metal oxide, nitrogen dioxide gas and
oxygen:

Both the carbonates and nitrates decompose at higher temperatures as the Group is
descended, in other words, thermal stability increases down the Group.

This trend is due to the size of the metal ion and its polarizing power. Small ions have
greater polarizing power than large ions, because the charge density of a small ion is
greater. Both the carbonate and nitrate anions are large, with diffuse electron clouds, and
this makes them easily polarisable. So the small magnesium ion can polarize the large
anion, attracting the electrons towards it — this distorts the shape of the anion, which
encourages decomposition. The large barium ion, however has little tendency to polarize the
anion, and decomposition is not favoured. The other metal ions fall between these two
extremes, and so the decomposition temperatures rise as the Group is descended. Another
factor to be taken into account is the stability of the metal oxide formed. The largest lattice
energy for a metal oxide is at the top of the Group, because both magnesium ions and oxide
ions are small and highly charged. So in addition to magnesium carbonate (nitrate) having a
distorted anion, the product of the decomposition is favoured.

2.4 The uses of some of the Compounds of Magnesium and Calcium

10
Magnesium oxide

Is a refractory material, which means that it is resistant to heat (its melting point is over
(2800°C). Its main use is in the lining of furnaces.

Calcium Oxide

Is also called lime or quicklime. It is used in cement, mortar and plaster manufacture, but its
main use is in agriculture. It is spread on the soil in vast quantities to reduce the acidity of the
soil.

Calcium Hydroxide
Is also called slaked lime or hydrated lime. A suspension of fine calcium hydroxide
particles in water is called lime water.
Because of its strong basic properties, calcium hydroxide has varied uses, such as

▪ A form of lime, in water and sewage treatment and improvement of acid soils
▪ An ingredient in whitewash, mortar, and plaster
▪ An alkali used as a lye substitute in no-lye hair relaxers
▪ A chemical depilatory agent found in Nair
▪ A reagent
▪ In the reef aquarium hobby for adding bio-available calcium in solution for calcium-using
animals such as algae, snails, hard tube worms, and corals (often referred to as
Kalkwasser mix)
▪ In the tanning industry for neutralization of extra acid.
▪ In the petroleum refining industry for the manufacture of additives to oils (alkilsalicatic,
sulphatic, fenatic)
▪ In the chemical industry for manufacture of calcium stearate
▪ In the food industry for processing water (for alcoholic and soft drinks)
▪ For clearing a brine of carbonates of calcium and magnesium in the manufacture of salt
for food and pharmacopoeia
▪ In Native American and Latin American cooking, calcium hydroxide is called “Cal.” Corn
cooked with cal becomes nixtamal, which is considered tastier and easier to digest.
▪ A filter
▪ In the petrochemical industry for manufacturing solid oil of various marks
▪ In the manufacture of brake pads

11
▪ In the manufacture of ebonite
▪ For preparation of dry mixes for painting and decorating
▪ In manufacturing mixes for pesticides
▪ In manufacturing a drug called “Polikar” for fighting decay (due to fungus) of fruits and
vegetables during storage
▪ A dressing in paste form used for anti-microbial effect during a dental root canal
▪ procedure

Calcium Carbonate
Calcium carbonate is a chemical compound, with chemical formula CaCO3. It is commonly
used medicinally as a calcium supplement or as an antacid. Calcium carbonate is the active
ingredient in agricultural lime. It is a common substance found as rock in all parts of the
world and is the main component of seashells and the shell of snails. It is usually the
principal cause of hard water.

The main use of calcium carbonate is in the construction industry, either as a building
material in its own right (e.g. marble) or limestone aggregate for road building or as an
ingredient of cement or as the starting material for the preparation of builder’s lime by
burning in a kiln. A common contaminate is magnesium carbonate.

Calcium carbonate is widely used as an extender in paints, in particular matte emulsion paint
where typically 30% by weight of the paint is either chalk or marble. Calcium carbonate is
also widely used as a filler in plastics. Some typical examples include around 15 to 20%
loading of chalk in uPVC drain pipe, 5 to 15% loading of stearate coated chalk or marble in
uPVC window profile. Fine ground calcium carbonate is an essential ingredient in the
microporous film used in babies’ nappies and some building films as the pores are nucleated
around the calcium carbonate particles during the manufacture of the film by biaxial
stretching.

Calcium carbonate is also used in a wide range of trade and DIY adhesives, sealants and
decorating fillers. Ceramic tile adhesives typically contain 70 to 80% limestone. Decorating
crack fillers contain similar levels of marble or dolomite. It is also mixed with putty in setting
stained glass windows, and as a resist to prevent glass from sticking to kiln shelves when
firing glazes and paints at high temperature.

12
Calcium carbonate is widely used medicinally as an inexpensive dietary calcium supplement,
antacid, and/or phosphate binder. It is also used in the pharmaceutical industry as a base
material for tablets of other pharmaceuticals.

Calcium carbonate is known as whiting in ceramics/glazing applications, where it is used as

a common ingredient for many glazes in its white powdered form. When a glaze containing
this material is fired in a kiln, the whiting acts as a flux material in the glaze. It is commonly
called chalk as it has been a major component of blackboard chalk. Chalk may consist of
either calcium carbonate or gypsum, hydrated calcium sulfate CaSO42H2O.

Group IV Elements

3.1 to 3.4

Variations in melting points and electrical conductivities in terms of structure and bonding

Carbon is most naturally found as graphite or diamond (its other allotrope is fullerite, which
consists of C60 molecules).

Diamond is a giant molecule with all carbon atoms bonded to four others by a single covalent
bond in a tetrahedral shape.
▪ Account for the melting point of diamond.
▪ Account for the electrical conductivity of diamond.

13
Graphite — each carbon atom is covalently bonded together to three others in layers of’
hexagonal rings joined together by weak van der Waals forces.
▪ Account for the melting point of graphite.
▪ Account for the electrical conductivity of graphite.

Silicon molecules have a similar shape to diamond, but due to the increasing metallic
property down the group, the electrons are not held as tightly and so a small proportion of
them can break free from the covalent bonds and delocalize throughout the solid structure.

Classified as a metalloid.
▪ Account for the melting point of silicon.
▪ Account for the electrical conductivity of silicon.
Germanium is again similar to diamond in shape, but more metallic than silicon leading to
better conductivity and a lower melting point. It is also classified as a metalloid.

Tin and lead have close packed metallic structures.

▪ Account for the melting point of tin and lead.
▪ Account for the electrical conductivity of tin and lead.

The Tetrachlorides

Each of the tetrachlorides consists as discrete molecules of general formula EC14. The
central Group IV element is attached to four chlorine atoms by four single covalent bonds.
The shape of the molecule is tetrahedral. They are all volatile liquids at room temperature.
The stability of the tetrachlorides decreases down the group; tin (with heating) and lead
(readily) will drop down to the +2 state forming SnCI2 and PbCl2 respectively.
▪ What is the bond angle in the tetrachloride?
▪ What type of hybridization occurs in the formation of the tetrachlorides?
▪ Account for the fact that they are all liquids.

Hydrolysis of the Tetrachlorides

(This has to be explained in terms of structure and bonding)

Carbon tetrachloride is immiscible with water and does not react with it. It forms a separate
layer underneath the water. There are two possible explanations for this:

14
1. Suppose a water molecule is going to react with the carbon tetrachloride. The reaction
would have to start by the water molecule’s oxygen attaching itself to the carbon atom
via the oxygen’s lone pair. A chlorine atom would get pushed off the carbon in the
process.

There are two problems with this.

First, the chlorines are so bulky and the carbon atom so small, that the oxygen can’t
easily get at the carbon atom.

2. The other problem is that there isn’t a convenient empty orbital on the carbon that the
oxygen lone pair can attach to. This is because carbon does not have any low lying
vacant orbitals (namely d orbitals) for the occupation by the electrons of water, so a
water molecule is unable to bond with it.

All of the other tetrachlorides are readily hydrolyzed by water.

For example when SiCL reacts with water the following occurs:

The products of the reaction are hydrogen chloride fumes and a white ppt of hydrated
silicon dioxide. In this reaction, the silicon atom in the compound is attacked by a lone
pair of electrons from the oxygen atom of a water molecule. For this reaction to occur,
there must be empty orbitals for these electrons to occupy. In the case of silicon and the
Group IV elements below it, the extra pair of electrons is accommodated using the empty
d orbitals available.

The oxides of Group IV

The most common oxidation number in Group 1V is +4 e.g. as in CO2 and SiO2. The state
with an oxidation number of +2 becomes increasingly stable with increasing atomic number.
For example when the elements are heated with oxygen they form the oxides

15
 ▪ What is the oxidation state of lead in PbO?

This is due to the inert pair effect which basically states that as the atomic radius gets larger
there is more of a tendency for the electrons in the s orbital to retain their position so that it is
only the two electrons in the p orbitals that participate in bonding. (The +2 oxidation state is
more stable than the +4 state). The elements in their +4 oxidation states therefore form
covalent compounds and those in the +2 state are predominantly ionic. Note that CO stands
outside the overall trend.

Properties of oxides of +4 oxidation states

16
Oxides of oxidation state +2

Co and SiO are both neutral oxides and as such do not react with acids or bases. SnO and
PbO) are amphoteric.

The stabilities of the +4 oxidation state oxides decreases down the group, but the stability’s
of the +2 oxidation state increase, until, in the case of lead, it is the more stable state.
Thermal Stability of the Oxides

17
C02, Si02, Ge02 and Sn02 are thermally stable even at high temperatures; these are the most
stable oxides of these elements. Pb02 decomposes, when warmed, into PbO, which is the
more stable state for lead.

EØ values and reactions of tin (II) and lead (II) ions

The uses of ceramics based on Silicon (IV) Oxide (SiO2)

18
19
Group VII Elements

4.1 Variations in physical properties of the elements

4.2 The relative reactivity of the elements as oxidizing agents

20
4.3 The reactions of the elements with hydrogen

21
4.4 The Relative Stabilities of the Halides

4.5 The reactions of the halide ions with:

22
31: Atomic and Physical Properties of Period 3

Atomic Properties

Electronic Structures

In Period 3 of the Periodic Table, the 3s and 3p orbitals are filling with electrons.
Na [Ne] 3s1

Mg [Ne] 3s2
Al [Ne] 3s2 3px1

Si [Ne] 3s2 3px1 3py1

P [Ne] 3s2 3px1 3py1 3pz1

S [Ne] 3s2 3px2 3py1 3pz1

Cl [Ne] 3s2 3px2 3py2 3pz1

Ar [Ne] 3s2 3px2 3py2 3pz2

In each case, [Ne] represents the complete electronic structure of a neon atom.

Atomic Radius

The Trend

The diagram shows how the atomic radius changes as you go across Period 3

The figures used to construct this diagram are based on:

▪ metallic radii for Na, Mg and Al;

▪ covalent radii for Si, P, S and Cl;
▪ the van der Waals radius for Ar because it doesn't form any strong bonds.

23
It is fair to compare metallic and covalent radii because they are both being measured in
tightly bonded circumstances.

The general trend towards smaller atoms across the period is NOT broken at argon.

Explaining the Trend

A metallic or covalent radius is going to be a measure of the distance from the nucleus to the
bonding pair of electrons.

From sodium to chlorine, the bonding electrons are all in the 3-level, being screened by the
electrons in the first and second levels. The increasing number of protons in the nucleus as
you go across the period pulls the bonding electrons more tightly to it. The amount of
screening is constant for all of these elements.

Electronegativity

Electronegativity is a measure of the tendency of an atom to attract a bonding pair of

electrons.

The Pauling scale is the most commonly used. Fluorine (the most electronegative element)
is assigned a value of 4.0, and values range down to caesium and francium which are the
least electronegative at 0.7.

The Trend

The trend across Period 3 looks like this:

Notice that argon isn't included. Electronegativity is about the tendency of an atom to attract
a bonding pair of electrons. Since argon doesn't form covalent bonds, you obviously can't
assign it an electronegativity.

Explaining the Trend

24
The trend is explained in exactly the same way as the trend in atomic radii.

As you go across the period, the bonding electrons are always in the same level - the 3-level.
They are always being screened by the same inner electrons.

All that differs is the number of protons in the nucleus. As you go from sodium to chlorine,
the number of protons steadily increases and so attracts the bonding pair more closely.

Physical Properties

Structures of the Elements

The structures of the elements change as you go across the period. The first three are
metallic, silicon is giant covalent, and the rest are simple molecules.

Three Metallic Structures

Sodium, magnesium and aluminium all have metallic structures.

In sodium, only one electron per atom is involved in the metallic bond - the single 3s
electron. In magnesium, both of its outer electrons are involved, and in aluminium all three.

The other difference you need to be aware of is the way the atoms are packed in the metal
crystal.

Sodium is 8-co-ordinated - each sodium atom is touched by only 8 other atoms.

Both magnesium and aluminium are 12-co-ordinated (although in slightly different ways).
This is a more efficient way to pack atoms, leading to less wasted space in the metal
structures and to stronger bonding in the metal.

A Giant Covalent Structure

Silicon has a giant covalent structure just like diamond. A tiny part of the structure looks like
this:

25
The structure is held together by strong covalent bonds in all three dimensions.

Four Simple Molecular Structures

The structures of phosphorus and sulphur vary depending on the type of phosphorus or
sulphur you are talking about. For phosphorus, I am assuming the common white
phosphorus. For sulphur, I am assuming one of the crystalline forms - rhombic or monoclinic
sulphur.

The atoms in each of these molecules are held together by covalent bonds (apart, of course,
from argon).

In the liquid or solid state, the molecules are held close to each other by van der Waals
dispersion forces.

Electrical Conductivity

▪ Sodium, magnesium and aluminium are all good conductors of electricity.

▪ Silicon is a semiconductor.
▪ None of the rest conducts electricity.
The three metals, of course, conduct electricity because the delocalized electrons (the "sea
of electrons") are free to move throughout the solid or the liquid metal.

26
Melting and Boiling Points
The chart shows how the melting and boiling points of the elements change as you go
across the period. The figures are plotted in Kelvin rather than °C to avoid having negative
values.

The Metallic Structures

Melting and boiling points rise across the three metals because of the increasing strength of
the metallic bonds.

The number of electrons which each atom can contribute to the delocalized "sea of
electrons" increases. The atoms also get smaller and have more protons as you go from
sodium to magnesium to aluminium.

The attractions and therefore the melting and boiling points increase because:

▪ The nuclei of the atoms are getting more positively charged.

▪ The "sea" is getting more negatively charged.
▪ The "sea" is getting progressively nearer to the nuclei and so more strongly attracted.

Silicon
Silicon has high melting and boiling points because it is a giant covalent structure. You have
to break strong covalent bonds before it will melt or boil.

The Four Molecular Elements

Phosphorus, sulphur, chlorine and argon are simple molecular substances with only van der
Waals attractions between the molecules. Their melting or boiling points will be lower than
those of the first four members of the period which have giant structures.

Phosphorus
Phosphorus contains P4 molecules. To melt phosphorus you don't have to break any
covalent bonds - just the much weaker van der Waals forces between the molecules.

27
Sulphur

Sulphur consists of S8 rings of atoms. The molecules are bigger than phosphorus molecules,
and so the van der Waals attractions will be stronger, leading to a higher melting and boiling
point.

Chlorine

Chlorine, Cl2, is a much smaller molecule with comparatively weak van der Waals
attractions, and so chlorine will have a lower melting and boiling point than sulphur or
phosphorus.

Argon

Argon molecules are just single argon atoms, Ar. The scope for van der Waals attractions
between these is very limited and so the melting and boiling points of argon are lower again.

CHEMICAL REACTIONS OF THE PERIOD 3 ELEMENTS

The reactions of the Period 3 elements from Sodium to Argon with water, oxygen and
chlorine.

Reactions with Water

Sodium

Sodium has a very exothermic reaction with cold water producing hydrogen and a colourless
solution of sodium hydroxide.

Magnesium

Magnesium has a very slight reaction with cold water, but burns in steam.

Magnesium hydroxide is formed as a very thin layer on the magnesium and this tends to stop
the reaction.

28
Magnesium burns in steam with its typical white flame to produce white magnesium oxide
and hydrogen.

Aluminium

Aluminium powder heated in steam produces hydrogen and aluminium oxide. The reaction is
relatively slow because of the existing strong aluminium oxide layer on the metal, and the
build-up of even more oxide during the reaction.

Silicon

There is a fair amount of disagreement in the books and on the web about what silicon does
with water or steam. The truth seems to depend on the precise form of silicon you are using.

The common shiny grey lumps of silicon with a rather metal-like appearance are fairly
unreactive. Most sources suggest that this form of silicon will react with steam at red heat to
produce silicon dioxide and hydrogen.

But it is also possible to make much more reactive forms of silicon which will react with cold
water to give the same products.

Phosphorus and Sulphur

These have no reaction with water.

Chlorine

Chlorine dissolves in water to some extent to give a green solution. A reversible reaction
takes place to produce a mixture of hydrochloric acid and chloric(I) acid (hypochlorous acid).

29
In the presence of sunlight, the chloric (I) acid slowly decomposes to produce more
hydrochloric acid, releasing oxygen gas, and you may come across an equation showing the
overall change:

Argon
There is no reaction between argon and water.

Reactions with Oxygen

Sodium
Sodium burns in oxygen with an orange flame to produce a white solid mixture of sodium
oxide and sodium peroxide.

For the simple oxide:

Magnesium

Magnesium burns in oxygen with an intense white flame to give white solid magnesium
oxide.

Aluminium

Aluminium will burn in oxygen if it is powdered, otherwise the strong oxide layer on the
aluminium tends to inhibit the reaction.

Silicon

Silicon will burn in oxygen if heated strongly enough. Silicon dioxide is produced.

30
Phosphorus

White Phosphorus catches fire spontaneously in air, burning with a white flame and
producing clouds of white smoke - a mixture of Phosphorus(III) Oxide and Phosphorus(V)
Oxide.

The proportions of these depend on the amount of Oxygen available. In an excess of

Oxygen, the product will be almost entirely Phosphorus(V) Oxide.

For the Phosphorus(III) Oxide:

For the Phosphorus(V) Oxide:

Sulphur

Sulphur burns in air or oxygen on gentle heating with a pale blue flame. It produces
colourless sulphur dioxide gas.

Chlorine and Argon

Despite having several oxides, chlorine won't react directly with oxygen. Argon doesn't react
either.

Reactions with Chlorine

Sodium

Sodium burns in chlorine with a bright orange flame. White solid sodium chloride is
produced.

Magnesium

Magnesium burns with its usual intense white flame to give white magnesium chloride.

31
Aluminium
Aluminium is often reacted with chlorine by passing dry chlorine over aluminium foil heated in
a long tube. The aluminium burns in the stream of chlorine to produce very pale yellow
aluminium chloride. This sublimes (turns straight from solid to vapour and back again) and
collects further down the tube where it is cooler.

32
33
34
35
36
37
38
39
40
41
42
43
44
45
 Sulphuric acid, of course, has all the reactions of a strong acid that you are familiar with
from introductory chemistry courses. For example, the normal reaction with sodium
hydroxide solution is to form sodium sulphate solution - in which both the acidic
hydrogens react with hydroxide ions.

46
47
48
49
50
51
52
53
54
55
56
32: Physical Properties of Group 2, 4, 7 Elements

Group 2 Elements
Beryllium to Barium

57
There is a large increase for the 3rd I.E. as the electron is now being removed from a
shell nearer the nucleus and there is less shielding.

58
OXIDES OF GROUP II ELEMENTS

Properties • ionic solids; except beryllium oxide which has covalent character

59
Sulphates- solubility decreases down the group

60
Physical Properties of Group IV Element

The elements of Group 4 are:

symbol electron configuration
carbon C [He]2s22p2
silicon Si [Ne]3s23p2
germanium Ge [Ar]3d104s2 4p2
tin Sn [Kr]4d105s2 5p2
lead Pb [Xe]4f14 5d106s2 6p2

Trends and patterns

1. The atomic radii increases down the group as the elements gain extra energy levels. The
increased shielding effect of the full inner shells more than outweighs the increased
nuclear charge and so the outer electrons are attracted less strongly.

2. Ionic radii increase down the group. Ions are much smaller than atoms because they
have lost the outer energy level and the nuclear charge is attracting four fewer electrons.

3. Ionization energies decrease down the group as the outer electrons become further from
the nucleus and more highly shielded from the inner shells.

The Inert-pair effect

Each element has four outer electrons ns2 np2. The shielding of the outer shell for C and Si is
quite efficient.
However, as we descend the group due to the presence of d and f electrons, which offer
poor shielding, the outer s electrons are withdrawn into the atomic core and begin to behave
as inner electrons.
Hence, Pb and Sn often behave as if they only have two outer electrons and show valencies
of +2 and +4.

Structure of the elements

C, Si, Ge are all giant covalent, Sn and Pb are metallic.

61
This trend reflects the decreased ionization energies and the increasing importance of
the inert-pair effect.

Properties related to structure

1. Melting and boiling points all decrease as we descend the group. There is a dramatic
decrease after Ge which reflects this change in structure.

2. Density and conductivity increase down the group reflecting the increasing metallic
character.

3. Electronegativity drops dramatically between C and Si due to the increased shielding

effect and weaker attraction for the outer bonding electrons. There is little decrease after
this due to the ineffectiveness of d and f electrons in shielding.

Oxidation states

There are two stable oxidation states in Group IV, +2 and +4.
The relative stabilities of the oxidation states vary within the group as shown in the following
graph.

+4 Oxidation State

a) All elements have four outer electrons and so the main oxidation state for most elements
is +4. The bonding in most compounds is covalent as too much energy would be needed
to form M4+ ion.
Only PbF4 and SnF4 are truly ionic. Most compounds have a tetrahedral arrangement
around the metal.

b) +4 is the most stable state for C, Si, Ge and Sn but is the least stable for Pb.
Compounds of Pb(IV) are easily reduced to Pb(II) and are strong oxidizing agents.

For example: PbO2(s) + 4HCl(aq) → PbCl2(s) + 2H20(l) + Cl2(g)

+2 Oxidation State

In this oxidation state only the p electrons are used in bonding and the s electrons exhibit the
inert-pair effect. It is most unstable for C and Si but is most stable for Pb.

62
Compounds of both Pb(II) and Sn(II) are common and the bonding in them ionic.
Compounds of C(II), Si(II), Ge(II) and Sn(II) are easily oxidised and are therefore strong
reducing agents.

For example: 2CO(g) + O2(g) → 2CO2(g)

Appearance

The expected similarity in appearance between elements in the same Group is much less
apparent in Group 14, where there is a considerable change in character on descending the
Group. Carbon is a dull black colour in the form of graphite, or hard and transparent in the
form of diamond; silicon and germanium are dull grey or black; tin and lead are a shiny grey
colour.

General Reactivity

In Group 4 the elements change from non-metallic in character at the top of the Group to
metallic at the bottom. Carbon is a non-metal, silicon and germanium are metalloids, and tin
and lead are typical metals. The general reactivity of the Group as a whole is therefore
difficult to ascertain, and the reactivity of each element must be considered individually.
Carbon exists in two important allotropic forms, diamond and graphite. Diamond has an
extended covalently-bonded structure in which each carbon atom is bonded to four others.
This compact, rigid arrangement explains why diamond is both extremely hard and
chemically inert. Graphite has a layer structure. Planes of covalently-bonded carbon atoms
are held together by weak van der Waals forces, and slide over each other easily.
Chemically, graphite is more reactive than diamond but still does not react easily. However, it
does oxidize at high temperatures and this is the reason why carbon is used in various forms
as fuel.

Silicon is chemically unreactive.

Germanium is also unreactive and not widely used, so will not be considered further. It does,
however, have excellent semi-conducting properties so may become more widely used in a
few years’ time.

Both tin and lead are generally unreactive metals. Tin has two common allotropes. At room
temperature the stable form is white tin; below 286.2K the stable form is grey tin. Tin has a
tendency to displace lead, and not vice versa as may be expected.

63
Occurrence and Extraction
Carbon, tin and lead can all be found in the elemental form in the Earth’s crust, and are
readily mined.
Silicon is found in mineral deposits and purified from them. Very pure silicon is required for
semi-conductors, and is obtained from sand via silicon (IV) chloride. This is first purified by
fractional distillation, then reduced to give the element. The silicon is then further purified by
zone refining, in which a molten zone is moved along a silicon rod several times, carrying
impurities to one end where they are removed.

Physical Properties
The physical properties of Group 14 elements vary quite widely from one element to another,
consistent with the increasing metallic character on descending the Group. The structures
change from giant molecular lattices in carbon and silicon to giant metallic lattices in tin and
lead, and this is the reason for the changes in physical properties. The change in bonding
from covalent to metallic down the Group causes a decrease in melting point, boiling point,
heat of atomization and first ionization energy. At the same time, the increasing metallic
character causes a general increase in density and conductivity.
Diamond has a very high refractive index (the reason for its sparkle) and this, along with its
rarity, has made it valuable as a jewel. However, it is also the hardest natural substance
known and so is important industrially.
The most important physical property of silicon is that it is a semi-conductor. Small silicon
chips, just a few millimetres square, have revolutionized the computer and microprocessor
industries.
Tin and lead, as typical metals, are good conductors of electricity.

Chemical Properties
In general, chemical reactivity increases on descending the Group.
The first member of the Group, carbon, is strikingly different from the others as it has the
unique ability to form stable compounds containing long chains and rings of carbon atoms.
This property, called catenation, results in carbon forming an enormous range of organic
compounds. The ability to catenate results from the C-C bond having almost the same bond
energy as the C-O bond, so that oxidation of carbon compounds is energetically favourable.
Also, the small size of the carbon atom allows two carbon atoms to approach close together
and allow overlap of p-orbitals, so that multiple bonds can be formed. The organic
compounds formed from carbon have a chemistry entirely different to any inorganic
counterpart.

64
The C-C and C-Si bond energies are very similar, so many organo-silicon compounds are
known. Silicon does not, however, form multiple bonds.

Silicon is unreactive chemically because an oxide layer seals the surface from attack, and
high temperatures are required for oxidation to occur. Silicon does, however, react with
fluorine at room temperature. It is not attacked by aqueous acids, but does react with
concentrated alkalis.

Tin and lead are quite easily oxidized, tin usually to tin(IV) and lead to lead(II). Both tin and
lead reduce the halogens.

Oxides

There are many oxides of Group 14 elements. The more common ones are:

CO (gas), CO2 (gas), SiO2 (solid), SnO2 (solid), PbO (solid), Pb3O4 (solid), PbO2 (solid).

Oxides with a lower oxidation number become more stable going down the Group. Carbon
dioxide is essential to life as it is the source of carbon for plants. During photosynthesis
carbon is combined with water to form carbohydrates. Solid carbon dioxide sublimes directly
to a gas, so is widely used as a cheap refrigerant.

Silicon forms a strong bond with oxygen in silica, SiO2, one form of which is quartz. Sand is
impure quartz. Oxoanions derived from silica are called silicates. They are very common in
nature and have structures based on SiO4 tetrahedra. One material containing these is
asbestos.

CO2 is acidic, as is CO under extreme conditions. SiO2 is acidic; it reacts with hot
concentrated alkali. SnO, SnO2, PbO and PbO2 are all amphoteric.

Halides

All the elements of Group 14 form tetrahalides, but only tin and lead form dihalides. The
tetrahalides are covalent tetrahedral molecules whereas the dihalides are best regarded as
ionic.

65
Hydrides

The hydrides of carbon are the hydrocarbons - organic compounds.

Silicon forms a series of hydrides called the silanes, with the general formula SinH2n+2.

Oxidation States and Ionization Energies

Group IV elements exist in two oxidation states, +2 and +4. There is a steady increase in the
stability of the +2 oxidation state on descending the Group.

The elements in this Group have four electrons in their outermost shell, two s electrons and
two p electrons. The first four ionization energies rise in a fairly even manner, and the fifth
ionization energy is very large, reflecting the removal of an electron from a filled level nearer
to the nucleus. Compounds of tin and lead in which the Group 14 element has an oxidation
number +2 are regarded as ionic. In these compounds, the Sn2+ and Pb2+ ions are formed by
loss of the outermost two electrons, whilst the two s electrons remain relatively stable in their
filled sub-shell. This is called the "inert pair effect".

Industrial Information

The industrial importance of carbon in petrochemicals is immense. These hydrocarbons are

used extensively in almost all areas of modern civilization; clothing, dyes, fertilizers,
agrochemicals, fuels and new materials.

Silicon also contributes to new technology in the silicon chip, which has revolutionized the
computer and high-tech industries. Germanium is, like silicon, a semi-conductor used in
similar devices, but it is less widely used.

Tin and lead have more traditional industrial uses. Tin is used as a coating for other metals
to prevent corrosion, such as in tin cans, but it is in alloys that tin is used most extensively.
These include bronze, soft solder, type metal, phosphor bronze and pewter. Lead is used in
great quantities in storage batteries. It is also used in cable covering, for roofing in buildings
and for radiation shielding. It was used in the manufacture of tetraethyl lead, an anti-knocking
compound added to petrol, but this was shown to be an environmental hazard.

66
Trends in Group VIIA (Halogen) Elements

Properties of Group VII Elements

Trends in Properties of Group VII Elements:

The halogens are diatomic molecules that exist in group 7 (VII) of the periodic table.
They have the following physical properties:

State at Boiling point Atomic radius Ionic radius

Symbol Name Formula
r.t.p. (°C) (pm) (pm)
Pale yellow
Fluorine -188 72 136
gas
Pale Green
Chlorine -34.7 99 181
gas
Bromine Brown liquid 58.8 114 195
Dark grey
Iodine 184.0 133 216
solid

They also have many common properties:

• They are coloured.

• They exist as diatomic molecules.

• Melting points increase as you go down group 7.

• They are toxic.

• The reactivity decreases as you go down group 7.

• all Group VII metals have 7 valence electrons (7 electrons in the highest energy level)

• atomic radius increases down the Group as successive 'electron shells' (energy levels)
are filled

67
• Electronegativity (the relative tendency shown by a bonded atom to attract electrons to
itself) decreases down the group as the elements become more metallic in nature.
(Typically, metals have low electronegativity, little ability to attract electrons, while non-
metals have high electronegativity, greater ability to attract electrons). The reactivity of
Group VII elements is related to the element's ability to attract electrons, so the greater
the electronegativity, the more reactive the Halogen. So, chemical reactivity of Group VII
elements decreases down the Group, from the most reactive (Fluorine) to the least
reactive (Iodine).

• Down the Group, first ionization energy (the energy required to remove 1 electron from
the gaseous atom) decreases. As the atomic radius increases and the electron is further
from the nucleus it is less attracted to the nucleus (electron is said to be 'shielded')

• Melting point and boiling point increase down the Group as the elements become more
metallic in nature.

• There is a gradation in color going down the group, the elements become darker in
colour as they become more metallic in nature. Similarly there is a gradation in physical
appearance at STP, from gas to liquid to solid, as the elements become more metallic in
nature.

Chemical tests:
Identification of the halides

Chloride Bromide Iodide

Off-white Yellow
Addition of White precipitate
precipitate precipitate
Addition of dilute ammonia Precipitate
No change No change
solution dissolves
Addition of conc. ammonia Precipitate Precipitate
No change
solution dissolves dissolves

68
Reactions of halide salts with H2SO4
Chloride salts
Reaction
Oxidation state -1 +6 +6 -1
Bromide salts
Reaction
Oxidation state -1 +6 +6 -1

Reaction
Oxidation state -1 +6 +4 0
Iodide salts
Reaction
Oxidation state -1 +6 +6 -1

Reaction
Oxidation state -1 +6 +4 0

Reaction
Oxidation state -1 +6 -2 0

As it can be seen, as you descend the group the halide ions become more easily oxidized. In
fact ions are not oxidized at all with . Hence from the equations we can conclude
that the reducing power of the halide ions increase going down the group.

The chlorate (I) and chlorate (V) ions

There are two oxo-anions of chlorine each with different oxidation numbers:
The chlorate(I) ion – (where chlorine is in the +1 state)
The chlorate (v) ion – (where chlorine is in the +5 state)

69
Disproportionation

This occurs when a species is simultaneously oxidized and reduced. Chlorine undergoes this
in an alkaline environment:

The chlorate (I) ion also undergoes disproportionation but on heating:

The halogens as oxidizing agents

As you descend group 7, the halogens become less effective as an oxidizing agent. This
property can be used in the extraction of bromine from seawater. If Chlorine gas is passed
through seawater then the bromide ions are oxidized to bromine. Therefore Cl2 is a better
oxidizing agent than bromine.

70
33: Halogens in solution

The halogens dissolve in or react with water to varying extents and show a variety of
behaviours. The nature of the behaviour depends largely on the strength of the halogen as
an oxidant. For example, fluorine oxidizes water vigorously. The other halogens undergo a
series of reactions in which higher halogen oxidation states are reached.

Fluorine plus water

Unlike the other halogens, fluorine oxidizes water to oxygen, i.e.

Small amounts of hydrogen peroxide H2O2 and oxygen difluoride OF2 are also formed. The
solution contains essentially no dissolved fluorine gas, as it all reacts.

Chlorine plus water

Chlorine dissolves in water to give chlorine water Cl2 (aq), and some chlorine then reacts
with the water. Some oxidation of water occurs, especially in bright light, but the main
reaction is disproportionation, which is a reaction in which a species is both oxidized and
reduced:

The product HClO (aq) is called hypochlorous acid.

Hypochlorous acid and hypochlorite ion

Aqueous hypochlorous acid is a weak acid that ionizes to give the hypochlorite ion ClO−:

The hypochlorite ion ClO− contains chlorine with an oxidation number +1. It is an oxidant,
especially in acidic solution. It will, for example, oxidize iodide ion to iodine:

71
The hypochlorite ion acts as a powerful disinfectant and bleach. Disinfectant action depends
on its ability to oxidize organic material and thereby to disrupt the life processes of bacteria.
Sodium hypochlorite is the active constituent in domestic bleaches and sterilizing fluids (e.g.
Milton). ‘Bleaching powder’ contains calcium hypochlorite, and is used commercially for
water treatment and for bleaching paper and textiles. Bleaching action depends on the ability
of hypochlorite ions to break up the structures of organic colouring matter.

Sodium hypochlorite
This substance can be made commercially by the electrolysis of cooled brine. The
electrolysis cell is arranged so that the chlorine produced at the anode mixes with the
sodium and hydroxide ions in the solution.

Testing for chlorine. Chlorine gas bleaches a piece of moist litmus paper held in it. The
paper must be moist so that the chlorine may dissolve and react to form hypochlorous acid,
which bleaches the paper. A red colour (indicating acidity) may be seen very briefly first.

Hypochlorous acid is a good bactericide. ‘Chlorine’ is therefore used to kill bacteria in

swimming pools and drinking water. As you might expect, it is important to use the
optimum quantities in each case, with increased concentrations being required in
swimming pools. The source of chlorine is often granulated calcium hypochlorite
Ca(ClO)2 or tablets of ‘Trichlor’.

Chlorine plus cold dilute aqueous sodium hydroxide

The equilibrium mixture of chlorine in water is acidic. If aqueous base is added, the
equilibrium is shifted much further to the right. For example, sodium hypochlorite is produced
when chlorine reacts with cold aqueous sodium hydroxide:

Similarly, the reaction between chlorine and aqueous calcium hydroxide forms calcium
hypochlorite:

72
A solution of hypochlorite ion disproportionate at temperatures above about 75 °C to form
chloride ion Cl− and chlorate ion ClO3−. Note again the changes in oxidation state:

Do not mix with acid!

Some toilet cleaners used to contain solid calcium hypochlorite Ca(ClO)2, the
approximate formula for ‘bleaching powder’. The label usually warned against ‘mixing with
other proprietary cleaners which may contain acid’. Some limescale removers contained
30% hydrochloric acid. If these two cleaning chemicals were used together, an
unpleasant mixture resulted that reacts according to the following chemical equation:

Choking fumes of poisonous chlorine gas were given off! The acid reverses the
equilibrium for the reaction of chlorine with water.
Decomposition

The hypochlorite ion slowly decomposes on standing as a result of two separate

reactions. The first involves disproportionation to chloride and chlorate ClO3−:

The second reaction evolves oxygen gas, and is observed especially in sunlight:

Bromine plus water or aqueous sodium hydroxide

Bromine undergoes a similar reaction with water to that of chlorine. The result is hydrobromic
acid HBr(aq) and hypobromous acid HBrO(aq):

73
 However, the equilibrium lies far to the left. Unless the solution is kept at around 0°C, the
hypobromite ion BrO− disproportionates further to give bromide ion Br− and bromate ion
BrO3−:

Reacting aqueous bromine with aqueous sodium hydroxide encourages the

disproportionation and increases the concentration of bromate ion.

Iodine plus water or aqueous sodium hydroxide

Iodine has very low solubility in water. However, it dissolves in water containing a high
concentration of iodide ions, e.g. KI(aq). An equilibrium is established in which iodide ion
reacts with iodine to form the triiodide ion:

The solution behaves as if it is a solution of I2(aq).

The concentration of HIO(aq) in this solution is negligible. Reacting iodine with aqueous
sodium hydroxide does not increase the concentration of hypoiodite ion IO−(aq). This
species disproportionates to give the iodate ion IO3−:

SUMMARY
• Fluorine oxidizes water to give oxygen and hydrofluoric acid.

• Chlorine and bromine dissolve in water and disproportionate to give hypochlorous and
hypobromous acids HXO.

• The concentrations of the hypohalite ions ClO− and BrO− may be increased by reacting
the halogen with a base, e.g. Cl2(g) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H20(l)

• The hypohalous acids are weak acids with stabilities in the order HClO → HBrO → HIO.

• Flypochlorite ion disproportionates to form chloride ion 3ClO−(aq) → 2Cl(aq) + ClO3−(aq)

74
34. Transition elements

Similarities between the d-block elements

Introduction

The d-block elements are sometimes called the transition elements. We have seen that
elements in the s-and p-blocks tend to have strong similarities to other members of their
group and that there are noticeable trends as we move along a period. In the d-block, the
elements show considerable similarities to one another even as we move across a period.
There are four main facets of the chemistry of d-block elements: their redox chemistry, the
colours of their compounds, their catalytic activity and their ability to form complexes -
compounds in which the metal ion is surrounded by other atoms or ions. The elements
themselves are particularly useful to us because they are relatively unreactive, mostly strong,
metals.

Transition or d-block Elements

Some of these are shown in Figures 1 and 2. The elements in each d-series are remarkably
similar to one another in size and also in first ionization energy. These similarities can be
explained by looking at their electronic structures.

Figure 3 shows the energy levels of the first few orbitals drawn so as to show their distance
from the nucleus. The electron arrangement of calcium is shown. The next level to be filled is
3d, which is where the first d-series starts with scandium.

75
Notice that although the 3d orbital is slightly higher in energy, it is closer to the nucleus than
4s. So the next ten electrons will go into the 3d orbitals, but the outer electrons will still be in
4s. This explains the similarities of the d-block elements. They all have the outer electron
arrangement 4s2 (see Figure 4). (This is not quite true as we shall see later, but it is a good
approximation.)

The first d-block element (scandium) has the electron arrangement [Ar]3d14s2, the next,
(titanium) is [Ar}3d24s2, the next (vanadium) [Ar]3d34s2 and so on. Each atom has one more
nuclear charge than the one before but the extra electron, being in 3d (an inner shell),
shields the nucleus quite effectively and the outer electrons ‘feel’ almost the same shielded
nuclear charge. So their sizes and first ionization energies are quite similar and so are many
other properties.

QUESTION: [Ar] represents the electron arrangement of argon. Write it out in full.
ANSWER: 1s22s72p63s23p6

Figure 1 A graph of atomic (covalent) radius against atomic number (van der Waals radius is
used for the inert gases)

76
Figure 2 A graph of first ionisation energy against atomic number

Figure 2 A graph of first ionisation energy against atomic number

77
Figure 3 The energies of orbitals showing their distances from the nucleus, The electron
arrangement of calcium is shown.

Figure 31.4 Electronic arrangements of the elements in the first d-series.

78
The arrangements of chromium, Cr, and copper, Cu, do not quite fit the pattern. 4s and 3d
are very close in energy and electrons can easily move from one to another. Their
arrangements occur because there is an extra stability associated with full (3d10) or half full
(3d5) d-shells. This is rather like the extra stability of full shells in the noble gases.

Transition Elements

You will often see the term transition elements used to refer to elements in the d-block of the
Periodic Table. The two terms are not quite the same. The formal definition of a transition
element is that it is one which forms at least one compound with a part full d-shell of
electrons. Since Scandium forms Sc3+, which is 3d0, in all its compounds, and zinc forms
Zn2+[3d10] in all its compounds, they are not strictly transition elements. However, they are d-
block elements.

Physical Properties of d-block Elements

We have seen that physical properties of d-block metals — for example, the first ionization
energy and metallic radius — vary relatively little across a period. The same applies to many
other properties like melting temperature, boiling temperature and hardness. The d-block
metals can be said to be typical metals, being good conductors of heat and electricity, hard,
strong, shiny, having high melting and boiling temperatures. One notable exception is
mercury, which is liquid at room temperature (Tm = 234 K). No simple explanation exists for
this oddity.

These physical properties together with fairly low chemical reactivity make these metals
extremely useful. Examples include iron (and its alloy steel) for vehicle bodies and to
reinforce concrete, copper for water pipes, and titanium for jet engine parts, which must
withstand high temperatures. Melting and boiling temperatures are shown in Figure 5. The
‘dips’ at calcium-(3d°), manganese (3d5) and zinc (3d10) are caused by the extra stability of
half full, empty and full d-shells. These electron arrangements make electrons less available
for contribution to the ‘pool’ for metallic bonding, thus weakening the metallic bond and giving
low melting and boiling temperatures.

79
Figure 5 Melting and boiling temperatures of the elements in the first d-series

Chemical Properties of d-block Elements

The chemistry of d-block metals has four main features which are common to all the
elements, except zinc and scandium, which are not typical.

1. Variable oxidation states. Typically, the d-block metals show more than one oxidation
state in their compounds (see Table 1). This is in contrast to the s-block metals which
have a fixed oxidation number in all their compounds (Ox = +1 for Group I and Ox = +11
for Group II).

2. Complex formation. The d-block elements form complexes. A complex is a compound

in which molecules or ions called ligands form dative covalent bonds to a metal atom or,
more usually, a metal ion.

3. Colour. The majority of transition metal ions are coloured. Some examples you may be
familiar with are: hydrated copper (II) sulphate, blue; nickel(II) carbonate, green, iron(III)
chloride, brown. Contrast this with the s-block metals whose ions are colourless. Thus,
sodium chloride, potassium nitrate, calcium oxide are all white. Zinc and scandium ions
are also colourless.

80
4. Catalysis. Many transition metals and their compounds show catalytic activity. For
example, iron in the Haber process, vanadium(V) oxide in the Contact process and
manganese(lV) oxide for the decomposition of hydrogen peroxide.

QUESTIONS: 1. Sodium çhromate, Na2CrO4, is yellow. Explain how this can be the case.
2. What are the products of (a) the Haber process and
(b) the Contact process?
ANSWERS: 1. The chromate ion, Cr042− is yellow — it contains a transition metal.
2. (a) ammonia, (b) sulphuric acid

Variable Oxidation States

A typical d-block element can show a variety of oxidation states in different compounds as
shown in Table 1 for the first transition series.
The more commonly encountered states are shown in red, though not all are stable. Some
patterns emerge:
• Except for scandium and zinc (which are not transition metals) all the elements show the
+I and +II oxidation states which correspond to forming bonds using only the 4s
electrons.
• There is an increase in the maximum oxidation number from scandium to manganese.
For these metals, the maximum oxidation number corresponds to both 4s electrons and
all the 3d electrons being used in bond formation. For example, manganese, 3d54s2,
forms manganese (VII).
• From manganese to zinc, the maximum oxidation number decreases. This suggests that
both 4s electrons and the unpaired d electrons can be used to form bonds. For example,
cobalt (3d74s2) has three unpaired d electrons, so its maximum oxidation number in
compounds is +V (two 4s electrons and three unpaired d electrons].
Note that only the lower oxidation states actually exist as free ions, so that, for example,
Mn2+ ions exist but Mn7+ ions do not. In all Mn (VII) compounds the manganese is covalently
bonded (see Figure 6, for example).

81
Figure 6 Bonding in the Mn04− ion

Table 1 Oxidation numbers exhibited by the elements of the d-series in their compounds

The Anticlockwise Rule

Because the oxidation number of the d-block elements can vary in their compounds, they
take part in many redox (electron transfer) reactions. The anticlockwise rule, can help predict
what happens in these reactions.
For example, the redox chemistry of iron is fairly straightforward because the only important
oxidation numbers are 0 [Fe], +II [Fe2+] and +III [Fe3+].

We can look up the values for the half reactions:

and

and insert them on an −oxidation number diagram (Figure 7) with any other half reactions
that we are interested in, for example chlorine/chloride ions and hydrogen/hydrogen ions:

82
Figure 7 —Ox diagram for iron compounds

The anticlockwise rule tells us that half reactions at the top of the diagram will go from right
to left and drive any reactions below them from left to right. So if we look at the reaction
between Fe2+(aq) and Cl−(aq) we can predict that:

will go from right to left so we change the sign of , giving:

and

83
will go from left to right. Adding gives:

for this reaction is positive and almost +0.6 V, so the reaction will essentially go to
completion.
In the same way we can predict from the diagram that:

Complex Formation

A complex is formed when a transition metal ion is surrounded by other molecules or ions
which use lone pairs to form dative covalent bonds with the d-block metal. The molecules or
ions which form the dative bonds are called ligands. Ligands are negative ions or molecules
with a dipole, the negative end of which forms the dative bond. Ligands include: :Cl−, :NH3,
:OH−, :OH2.
The number of ligands that surround the d-block metal ion is usually four or six. Typical
complex ions include [Co(NH3)5]3+ and [CoCI4]2−:

In [Co(NH3)6]3+, since the

metal ion has a charge of
+3 and the ligands are all
neutral, the complex ion
has an overall charge of
+3. The geometry of the
ion is octahedral.

In [CoCl4]2− the metal ion has a charge of +2 and each of the four ligands has a charge of −1.
The complex ion has an overall charge of −2. The geometry is tetrahedral.

84
The number of ligands surrounding the metal ion is called the coordination number.
Coordination numbers of four and six are the most common. The usual geometries are
tetrahedral and octahedral respectively. A few complexes of coordination number four adopt
a square planar geometry. For example:

There are also linear complexes, especially of Ag+ ions. These include Ag(CN)2−, used in
electroplating, and Ag(S2O3)23− used in photography.
Notice that complex ions may have a positive or negative charge, or less commonly be
neutral.

QUESTION: What is the charge on the Ni in [Ni(CN)4]2−? The ligand is CN−

ANSWER: +2

Bonding in complex ions

In transition metal complexes, dative covalent bonds are formed by lone pairs on the ligands
donating electrons into the partly empty d orbitals of the d-block metal ion. This contrasts
with solvation (or hydration) of s-block metal ions, which may be surrounded by polar
molecules with the negative ends of their dipoles towards the positive metal ion. In these the
bonding is just the electrostatic attraction between the positive ion and the dipoles.

Polydentate ligands: chelation

Some molecules, called polydentate ligands, have more than one lone pair that can bond
to a transition metal ion. The ‘dentate’ part of the word comes from the Latin for tooth — the
ligands can ‘bite’ the metal ion more than once.

85
Bidentate ligands include the following:

• Ethane-1,2-diamine, sometimes called 1,2-diaminoethane or ethylene diamine:

Each nitrogen has a lone pair which can form a dative bond to the metal ion. The name of
this ligand is often abbreviated to ‘en’, e.g. [Cr(en)3]3+.

• Benzene-1,2-diol, sometimes called 1,2-dihydroxybenzene:

Both ligand sites of bidentate ions usually bond to the same metal forming a ring. However,
they can act as bridges between two metal ions.
An important polydentate ligand is 1,2-bis[bis(carboxymethyl) amino]ethane often still called
by its non-systematic name ethylenediaminetetraacetate or edta:

86
Did you know? Edta can be taken (under medical supervision) as an antidote to poisoning by
transition metals. The chelated ions are excreted in the urine.

This can act as a hexadentate ligand using lone pairs on each of the four O− ions and both
the nitrogens.
Complex ions with polydentate ligands are called chelates (pronounced key-lates) from the
Greek word for claw. Chelates can be used to effectively remove d-block metal ions from
solution.

Naming d-block Metal Complexes

Metal complexes are named by placing the name(s) of the ligand(s) (in alphabetical order if
there are more than one and ignoring prefixes like di-, tri-, etc. in deciding the alphabetical
order) before the name of the metal atom. If the overall complex has a negative charge this
is indicated by the suffix ‘-ate’. When the suffix ‘-ate’ is used, the Latin version of the metal
name is used (if there is one), so we have ‘cuprate’ and ‘ferrate’ rather than ‘copperate’ and
‘ironate’. The oxidation number of the metal is given in brackets at the end. The names used
for ligands are given in Table 2.

87
Table 2 Names of some ligands

For example:

The oxidation number of the metal is found by subtracting the total charge of the ligands
[including their signs] from the charge on the ion:

The names of any other ions are given in the usual way so we might have a solution of
potassium hexacyanoferrate(II) or hexaaquacobalt(II) chloride.

88
Isomerism in Complexes

Isomerism occurs when two or more compounds have the same molecular formula but a
different arrangement of theft atoms in space. Three different types occur in d-block metal
complexes:

Ionization Isomerism

Here ligands vary in theft bonding. For example, three compounds exist with the overall
formula CrCl3.6H2O. They are:

As well as by their colours, these complexes can be distinguished by addition of silver

nitrate. Only the free Cl− ions will react to form a precipitate with silver nitrate; those bonded
to the chromium (as ligands) will not. So 1 mole of compound I will react with 3 moles of
silver nitrate, 1 mole of compound 2 with 2 moles of silver nitrate and 1 mole of compound 3
with 1 mole of silver nitrate.

Geometrical (cis−trans) Isomerism

Here ligands differ in their position in space relative to one another. Compound 3 above also
illustrates geometrical isomerism. The complex is octahedral and two arrangements of the
ligands in space are possible (Figure 8).
In (a) the chloride ligands are next to one another — this is called the cis-form. In (b) the
chlorides are on opposite sides of the chromium atom — this is called the trans-form. So the
full names of the compounds are:
(a) cis-tetraaquadichlorochromium (III) chloride;
(b) trans-tetraaquadichlorochromium (III) chloride.

89
You may need to look at models to convince yourself that there are only two possible cis-
trans isomers of this compound.

Figure 8 cis−trans isomerism

Competition between Ligands: Displacement reactions and /Stability Constants

Some ligands may form stronger bonds than other ligands with a particular metal ion. In this
case, the better ligand will displace the poorer one.

For example, copper (II) sulphate dissolved in water forms the tetraaquacopper(II) ion
[Cu(H2O)4]2+ which is responsible for the blue colour of the solution. Addition of chloride ions
in high concentrations leads to the replacement of H2O ligands by Cl− ligands one at a time
(‘stepwise’):

90
The overall reaction is:

Each of the equilibria 1−4 lies somewhat to the right implying that Cl− is a better ligand than
H2O.
The equilibrium law expression for the overall reaction is:

(Remember: pure liquids do not appear in Kc, expressions). The overall equilibrium is well
over to the right and [CuCl4]2−(aq) predominates over [Cu(H2O)4]2+(aq). If concentrated
hydrochloric acid, which contains a high concentration of chloride ions, is added to copper
sulphate, the blue colour of [Cu(H2O)4]2+(aq) is replaced by the yellow-green of [CuCl4]2−(aq).
Kc is called the overall stability constant for [CuCl]2−(aq). The higher Kc is, the more stable
the complex.

Ammonia is an even better ligand than the chloride ion, Cl−. It will displace both water froth
[Cu(H2O)4]2+(aq) and Cl− from [CuCl4]2−(aq) forming the dark blue [Cu(NH3)4]2+(aq). The
equilibrium constant for the overall replacement of water by ammonia is:

The overall stability constant for [Cu(NH3)4]2+(aq) is larger than that for [CuCl4]2−(aq), so NH3
is a better ligand than either Cl− or H2O.

Colour of d-block Metal Compounds

Colours and colour changes are among the most striking aspects of d-block metal chemistry.
A good example is the reaction of zinc with a solution containing a vanadium(V) compound.
The solution gradually changes from the yellow of vanadium(v) to blue vanadium(IV) to

91
green vanadium(III) to the mauve of vanadium(II) as the zinc gradually reduces the
vanadium compounds (see the photograph).

Absorption of Light by d-block Metal Atoms

When electrons in a substance move from one energy level to a higher one, they absorb a
quantum of electromagnetic energy equal in energy to the gap between the two levels. The
frequency, v, of this is given by the equation E = hv where E is the energy gap and h
Planck’s constant. If v is in the visible region of the spectrum, this will result in the substance
being coloured. If a substance absorbs, say, green light, it will let through red and blue and
thus appear purple (see Figure 10). In an isolated atom, all five d orbitals have exactly the
same energy. However, when ligands approach the metal atom or ion, they affect the energy
levels of different d orbitals differently, raising some slightly and lowering some slightly.
In most cases the resulting energy gap between the d orbitals corresponds to frequencies of
electromagnetic radiation in the visible region of the spectrum, so most transition metal
compounds are coloured.

Figure 10 The d-block metal complexes look coloured because they absorb light of some
colours and let other colours through.

Electrons can only move from one d orbital to another if there are spaces in the d orbitals, so
Zn2+ compounds which have the electron arrangement 3d10 (i.e. the d orbitals are full) are
not coloured. Sc3+ compounds (3d°) have no d electrons and are therefore also colourless
(as are the compounds of s-block metals). The compound titanium (IV) oxide, TiO2, is also
colourless. The Ti4+ ion is also 3d°. Compounds of s-block elements which also contain a
transition metal like, say, potassium manganate (VII), KMnO4, may, of course, be coloured
because of the presence of the transition metal.

92
Chemical changes, such as replacing one ligand by another, or oxidizing or reducing the
metal ion, will slightly affect the energies of the d orbitals and produce a compound with a
different colour.
The colours of transition metal complexes can be used in analytical techniques. For
example, Fe2+ ions form a red complex with the bidentate ligand 1,10-phenantholine

The intensity of colour of this complex can be measured using a colorimeter and used to
determine the concentration of Fe2+ ions by comparison with a solution of known
concentration.

Catalytic activity
Transition metals as catalysts may be divided into two distinct groups;
• homogeneous catalysts which are in the same phase as the reactants and which
involve transition metal compounds
• heterogeneous catalysts where the catalyst is in a different phase from the reactants
and where transition metal elements or transition metal compounds may be involved

Homogeneous Catalysts
The reaction of peroxodisulphate(VI) ions oxidizing iodide ions to iodine and have explained
how the reaction is catalyzed by either Fe2+ or Fe3+ ions.

93
Fe2+ ions as catalyst

Peroxodisulphate ions oxidize Fe2+ ions to Fe3+ ions. These then oxidize I− to I2.

Fe3+ ions as Catalyst

I− reduces Fe3+ to Fe2+, which then reduces peroxodisulphate ions. Note that while the single
step reaction occurs between two negatively charged ions (peroxodisuiphate and iodide),
each of the steps in both of the catalyzed reactions occur between oppositely charged ions.
This helps to explain the increased rate.

Examples of possible catalysts include:

In practice, only Mn(VII) actually catalyses the reaction, a useful reminder that predictions
made by the anticlockwise rule can only suggest that a reaction is possible, not that it must
take place.

Heterogeneous Catalysts
Table 4 Some examples of heterogeneous catalysis involving d-block metals or their
compounds

94
Examples of the Chemistry of some d-block Elements

This section discusses the chemistry of selected d-block metals and their compounds.

Scandium

Scandium shows no typical transition metal properties. It forms only one oxidation state,
+III, apart from Ox = 0. The Sc-3+ ion is colourless because Sc3+ has no d electrons. The
metal is similar to calcium in its reactivity with water:

Vanadium

Redox Chemistry of Vanadium

Vanadium forms four important oxidation states: + II, + III, +IV and +V. All can be obtained
in aqueous solution. Table 5 summarizes the species present in acidic solution.
Simple aqueous ions V4+(aq) and V5+(aq) do not exist. Covalent bonds with oxygen atoms
are formed and the vanadium(IV) state is usually represented as VO2+(aq) and the
vanadium(V) state as VO2+(aq). Similar situations occurs with high oxidation states of other
transition metals.
An oxidation number diagram helps us to understand the aqueous redox chemistry of
vanadium. The one in Figure 13.

Table 5 Vanadium species in aqueous solution. The colours are shown in the photographs
below, which have been produced by reducing VO2+(aq) with zinc in acid solution shows the
potentials in acid solution. Half reactions involving vanadium compounds are in red.

95
Figure 13 −Ox diagram for some oxidation states of vanadium

96
From this we can make number of predictions.

These reactions can be followed by observing the colours of the different vanadium species
formed.

Oxides of vanadium

The known oxides of vanadium are shown in Table 6. Their properties illustrate a general
trend in the d-block where the acidity of the oxides increases with the oxidation number of
the metal. Vanadium(II) oxide and vanadium(III) oxide are basic, vanadium(IV) oxide
amphoteric and vanadium(v) oxide acidic.

97
Chromium

Chromium metal is bluish-white. It has a high melting temperature (2130 K) and is quite
resistant to chemical attack, hence its most familiar use as a shiny plating on car bumpers,
cycle handlebars, etc.

Redox Chemistry of Chromium

Chromium has an extensive redox chemistry, the most important oxidation states being Cr(II)
(blue), Cr(III) (green) and Cr(vi) (yellow/orange). In aqueous solution Cr(vi) exists in two
forms, the chromate(vi) ion, CrO42-, and the dimeric dichromate(vi) ion Cr2O72−. The orange
dichromate ion is stable in acid solution and the yellow chromate ion in alkalis, as shown by
the equilibrium below.

The chromate ion is tetrahedral, having a similar structure to the sulphate ion (Figure 14)
while the dichromate ion consists of two tetrahedral linked by a bridging oxygen.
Chromium (III) is the most stable oxidation state in aqueous solution. Chromium(II) is easily
oxidized to chromium(II) by oxygen and can only be prepared in the absence of air. If it is
prepared by reduction of chromium(vi) by zinc in acid solution, the hydrogen produced can
be used to exclude air. The electrode potentials in Figure 15 show that this reaction is
feasible.

The chromium(vi) state is powerfully oxidizing and Cr2O72+/H+ is often used as an oxidizing
agent in organic chemistry. The −Ox diagram shows that Cr2O72−(aq) can oxidize I− to I2,
− −
Br to Br2, but not Cl to Cl2. The diagram also shows that chromium (II) will reduce all the
halogens to halide ions.

Different oxidation states of chromium have different colours

98
Figure 15 −Ox diagram for some oxidation states of chromium

Oxides of Chromium

The two oxides of chromium, chromium(III) oxide, Cr2O3, and chromium(vi) oxide, CrO3, are
typical in that the oxide with the higher oxidation number is more acidic. Chromium(vi) oxide
dissolves in water to give chromic acid, H2CrO4. Chromium(III) oxide is amphoteric.
Chromium(III) oxide contains the Cr3+ ion while chromium(vi) oxide is covalently bonded.

99
Did you know? Chromic acid, which is both an add and an oxidizing agent is useful for
cleaning laboratory glassware

Manganese

Manganese metal is brittle and fairly reactive and thus has relatively few uses. It is, however,
important as a constituent of many alloys. In its compounds, manganese displays more
oxidation states than any other metal in the first d-series. All the positive oxidation states up
to +VII are known, VII, IV, and III being the most important.

Redox Chemistry of Manganese Compounds

Much of the redox chemistry of manganese compounds can be related to Figure 16.
values show that manganese should react with acids to give manganese(II) salts. The
reaction is observed.
Manganese(II), in the form of pale pink hexaaquamanganese(II) ions, [Mn(H2O)6]2+, is the
most stable oxidation state of manganese in aqueous solution, owing partly to its 3d 5
electron arrangement. It is precipitated out of alkaline solutions as insoluble pale pink
manganese(II) hydroxide, Mn(OH)2.

100
Figure 16 −Ox diagram for some oxidation states of manganese

101
Potassium manganate(vu) can be used in redox titrations to measure the concentration of
reducing agents. It needs no indicator as the end point is shown by the disappearance of its
purple colour.
The manganese (vi) state is represented in solution by the green manganate(vi) ion,
MnOn42−. In acid solution it disproportionates. This reaction is indicated in red on Figure 16
The overall reaction is:

This reaction does not occur in alkaline solution. Manganese(III) in acid solution
disproportionates to manganese(II) and manganese(IV).

Oxides of Manganese

These are summarised in Table 7.

Table 7 Oxides of manganese.

102
As the oxidation number of the metal increases, the usual trends of increasing acidity and
increasing covalency are seen.

Iron

Iron is without doubt the most important metal in present day society. Around 33 000 tonnes
are produced daily in the UK, most being used to produce steels — alloys of iron with up to
30% of other elements added to improve their properties. In many ways, iron is not an ideal
constructional metal especially as it corrodes quite readily. However, this disadvantage is
outweighed by its cheapness, the result of its abundance (it is the second most abundant
metal in the Earth’s crust) and relative ease of extraction. Also, alloying and heat treatment
produce steels with a remarkable range of properties.

Redox Chemistry of Iron

This is relatively simple because iron shows only two common oxidation states in its
compounds, iron(II) and iron(III). An −Ox diagram is shown in Figure 17. Of these two
states, Fe3+ is the more stable as it has a 3d5 electron arrangement. Solutions containing
Fe2+ are oxidized by air to Fe3+.
The −Ox diagram shows that metallic iron could react with acids to form Fe2+(aq) ions and
hydrogen, and this reaction does take place. Bromine will oxidize Fe2+(aq) but to Fe3+(aq) but
Fe3+(aq) will oxidize I− (aq) to iodine.

103
Figure 17 −Ox diagram for some oxidation states of iron

Rusting

This is probably the most important redox reaction of iron Metallic iron is converted in the
presence of oxygen and water to rust (hydrated iron(III) oxide, Fe2O3.xH2O).
The rusting or corrosion of iron is an electrochemical process in which a cell is set up within
the metal (Figure 18).

104
Figure 18 The electrochemical rusting of iron

In any piece of iron, some areas will tend to accept electrons and others to give them away.
Such areas may be caused by impurities in the iron. A more reactive impurity like zinc would
release electrons better than iron, and be negative, while a less reactive impurity like copper
would tend to form a positive area. Most iron has impurities but even in very pure iron,
positive and negative areas can be produced by less obvious factors such as stress caused
by bending the metal and by uneven oxidation of the surface.
If the iron surface is covered with water, which contains dissolved oxygen from the air, the
following reactions can take place:

The electrons produced by the first reaction flow through the iron (which, of course, is a good
conductor) to take part in the second reaction. The Fe2+(aq) and OH−(aq) ions diffuse away
through the solution and where they meet, they react to give iron(II) hydroxide:

This is then oxidized by dissolved oxygen to iron(III) hydroxide which forms hydrated iron(III)
oxide, which is rust:

105
So rusting takes place only in the presence of air and water. It is accelerated by dissolved
ionic salts which make the water a better electrical conductor.

The Aqueous Chemistry of Iron Ions

Tests for iron ions

Both Fe2− and Fe3+ exist in aqueous solution as octahedral hexaaqua ions. [Fe(H 2O)6]2− is
pale green and [Fe(H2O)6]3+ is pale brown, and dilute solutions are hard to tell apart. A
simple test to distinguish the two is to add dilute alkali which precipitates the hydroxides,
whose colours are more obviously different.

Two other colour reactions provide tests to distinguish Fe2+ from Fe3+ ions.
• Addition of potassium thiocyanate (K+ + SCN−) to [Fe(H2O6)]3+ produces the blood-red
pentaaquathiocyanate iron(III) ion.

The colour of the ion is very intense and can be used to detect very small
concentrations of Fe3+(aq).
• The test for Fe2+(aq) is the formation of a deep blue colour, Prussian blue, on addition
of potassium hexacyanoferrate(Ill).

The Acidity of Aqueous Iron Ions

Solutions of Fe2+(aq) are not appreciably acidic, whereas a solution of Fe3+(aq) (pKa = 2.2) is
a stronger acid than ethanoic acid (pKa = 4.8). This is because the Fe3+ ion is both smaller

106
and more highly charged than Fe2+ making it more strongly polarising. So in the
[Fe(H2O)6]3+(aq) ion the iron strongly attracts electrons from the oxygen atoms of the water
ligands thus weakening the O—H bonds in these water molecules. These will then readily
donate H+ ions making the solution acidic (Figure 19).

Figure 19 The acidity of Fe3+(aq) ions

The acidity of the aqueous Fe3+ ion explains why iron(III) carbonate does not exist, but
iron(II) carbonate does. The Fe3+ ion is sufficiently acidic to react with the carbonate ion to
form hydrated iron (III) hydroxide.

Copper

Copper is an extensively used metal. UK consumption is almost 400 000 tonnes per year,
most of which is obtained from recycling. New copper is extracted from sulphide ores,
Copper’s lack of chemical reactivity and ease of working makes it suitable for plumbing pipes
and fittings, while its main use is as an electrical conductor. It is a constituent of many alloys
such as brass, gunmetal and bronze.

107
Redox Chemistry of Copper

Copper forms only two stable oxidation states, copper(I) and copper(II) in its compounds
(see Figure 20).

Copper(I) has a 3d10 electron arrangement and therefore is not transitional. As would be
expected, most of its compounds are white although its best known compound, copper(I)
oxide. Cu2O, is red- brown.

Copper(II) (3d9) is transitional and most of its compounds are blue in aqueous solution
because of the hydrated copper ion. Copper (II) oxide, CuO, is black.

In aqueous solution Cu+(aq) will disproportionate to Cu2+(aq) and Cu(s) as shown by the
anticlockwise rule (see Figure 20).

Ligand displacement reactions of copper with ammonia is complicated by the precipitation of

insoluble, pale blue copper(II) hydroxide. An aqueous solution of ammonia contains OH−(aq)
ions due to the equilibrium:

These precipitate copper hydroxide:

On adding excess ammonia, the copper dissolves as the tetraamine copper(II) ion which is a
very dark blue:

108
Figure 20 —Ox diagram for some copper compounds

Zinc

Zinc metal has the outer electron arrangement 3d104s2. It forms only one oxidation state,
Zn(II) which is 3d10. The metal is therefore non- transitional, its compounds typically being
white. Zinc does, however, form complexes such as the tetrahedral [Zn(OH)4]2−(aq),
[Zn(NH3)4)2+(aq), [ZnCl4]2−(aq).

109
35. Qualitative Analysis

IDENTIFYING GASES

110
IDENTIFYING IONIC SUBSTANCES

111
 TESTS FOR CATIONS

112
TEST FOR ANIONS

113
114
Answer the following questions

1. The following table shows the tests that a student performed on a aqueous solution of
Compound M and the interferences that were made.

Complete the middle column to show the possible observations from which the interferences
were made. In the space provided, write the ionic equation for the reaction occurring in (ii).

Test Observation Inference

(i) To a sample of solution Pb2+, Al3+, Zn2+, may be
M, aqueous sodium present.
hydroxide was added
slowly, until there was no
further change.
Pieces of moist red and NH4+
blue lithmus were held at
the top of the tubes
(ii) To a second sample, No Zn2+ present.
aqueous ammonia was Pb2+, Al3+ may be present
added until there was no
further change.
(iii) To a third sample, a few Pb2+ present.
drops of potassium
iodide solution were Ionic equation
added.
(6 marks)

2. A student conducts a number of tests on at aqueous solution of compound X. The

inferences and observations made are recorded in Table 2 below. Fill in the missing
observations and interferences.

115

Test
(i) To 1ml of solution X is
added a few copper
turnings, followed by
concentrated sulphuric
acid.
(ii) To 1 ml of solution X is
added dilute nitric acid
followed by aqueous
silver nitrate.
Aqueous ammonia is
next added until in
excess.
(iii) To 1 ml of solution X is
added aqueous lead
nitrate solution.
(iv) To 1 ml of solution X is
added aqueous ammonia
until in excess.
(v) To1 ml of solution X is
added aqueous sodium
hydroxide solution until in
excess.
(vi) To 1 ml of solution X is
added aqueous sodium
hydroxide and the
solution heated.
116
TABLE 2: RESULTS OF TESTS
Observation Inference
Brown gas evolves which
turns moist blue lithmus red.
(1 mark)
I- ions present
I- ions confirmed
(2 marks)
A bright yellow precipitate
forms. (Ionic equation required)
(2 marks)
Cu2+ ions present.
(2 marks)
Cu2+ ions present.
(2 marks)
Colourless gas with pungent
odour evolves which
a) turns moist red litmus blue (Ionic equation required)
b) gives dense White fumes
with glass rod dipped in (Ionic equation required)
Conc. HCl. (3marks)
3. A student conducts a number of tests on an aqueous solution of Compound X. The
observations made are recorded in Table 2 below. Complete Table 2 by filling in the
inferences that could be made based on the observations recorded.

TABLE 2: RESULTS OF TESTS ON A SOLUTION OF COMPOUND X

Test Observation Inference

To a sample of a solution of
X, dilute nitric acid is added
followed by a few drops of
silver nitrate solution.
To a sample of a solution of
X, aqueous sodium
hydroxide is added until in
excess.
To a sample of a solution of
X, a few drops of acidified
aqueous potassium
manganate (vii) solution are
added and the solution
heated.
To a sample of a solution of
X, a few drops of barium
chloride solution followed by
dilute hydrochloric acid are
added.
A white precipitate which
turns grey black in light is
formed. (1 mark)
(Ionic equation required)
(1 mark)
A pale blue gelatinous
precipitate is formed which is
insoluble in excess.
(1 mark)
The potassium maganate
(Vii) solution is decolourized.
(1 mark)
A white precipitate is formed.
The precipitate dissolves in
acid.
(1 mark)

117
Test Observation Inference
To a sample of solution Y, No precipitate formed.
dilute hydrochloric acid was
added, followed by a few
drops of silver nitrate
solution.
To s sample of solution Y, White precipitate is formed.
dilute hydrochloric acid was
added followed by a few
drops of barium chloride
solution.
Ta a sample of solution White precipitate, soluble in
Y, sodium hydroxide excess.
solution was added until
in excess. The mixture No effect on blue lithmus, red
was warmed and gas tested lithmus turned blue.
with blue and red litmus.
To a sample of solution Y, White precipitate, insoluble in
aqueous ammonia was excess.
added, until in excess.
To a sample of solution Y, No yellow precipitate
some potassium iodide
solution was added.

(vii) Which metal ion was present? _______________________________________

(viii) Give a reason for your answer _______________________________________

________________________________________________________________

4. TABLE 2: RESULTS OF TESTS ON SOLID Q

118
 (v) Suggest the possible identity of Q. (1 mark)

5. Table 3 presents some information on the reactions of Compound A and copper metal
with various reagents. Use the information in Table 3 to answer the questions that follow

TABLE 3 SOME REACTIONS OF COMPOUND A AND COPPER

119
120
6. A student conducted a number of tests on a solid Y. The observations made are
recorded on the table below. You are required to fill in the interferences that could be
made on the observations recorded.

121
 TABLE 1: RESULTS OF VARIOUS TESTS ON SAMPLE Y

7. A student carried out a number of tests on a solid labelled, R, which is mixture of two
compounds. The observations made are recorded in the table below. You are required to
fill in the inferences that could be made based or’ the observations recorded.

122
123
124