Chapter 9 – Inorganic Chemistry

The outer electron configuration is a periodic function... it repeats every so

often

Because many physical and chemical properties are influenced by the outer
shell configuration of an atom, it isn’t surprising that such properties also
exhibit periodicity...

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 • atomic radius
• ionic radius
• ionisation energy
• electron affinity
• electronegativity
• electrical conductivity
• melting point and boiling point

The first two periods in the periodic table are not typical...
Period 1 (H, He) contains only two elements
Period 2 (Li - Ne) elements at the top of each group have small sizes
and high I.E.values
Period 3 (Na-Ar) is the most suitable period for studying trends

1 2
Group(s) s block I and II end in s or s
1 6
p block III, IV, V, VI, VII and 0 end in p to p
1 10
d block Transition elements end in d to d
f block Actinides and Lanthanides end in f

2
 Bonding and Structure:

Moving from left to right the elements go from highly electropositive metals through
metalloids with giant structures to the simple molecular structure of non-metals.
Na Mg Al Si P4 S8 Cl2 Ar
< - - - metals - - - > metalloid < non metals (simple molecules)
>
Typical properties Metals Non-metals
Appearance solids - shiny when cut gases, liquids, dull solids
Hardness malleable and ductile brittle
Electrical conductivity excellent poor
Melting point high low

Not every element satisfies all the criteria. For example...

• carbon (graphite) is a non-metal which conducts electricity
• carbon and silicon have high melting points
• mercury is a liquid at room temperature and pressure

3
As you can see from the diagrams, the same atom could be found to have
a different radius depending on what was around it.

The left hand diagram shows bonded atoms. The atoms are pulled closely
together and so the measured radius is less than if they are just touching.
This is what you would get if you had metal atoms in a metallic structure, or
atoms covalently bonded to each other. The type of atomic radius being
measured here is called the metallic radius or the covalent radius
depending on the bonding.

The right hand diagram shows what happens if the atoms are just touching.
The attractive forces are much less, and the atoms are essentially
"unsquashed". This measure of atomic radius is called the van der Waals
radius after the weak attractions present in this situation.

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{From Chemguide.co.uk}

Ionic Radius:

Trends in the ionic radius: positive ions

• The ionic radii of positive ions (cations) are smaller than their corresponding
atomic radii.
• This is due to loss of whole valence shell of electrons resulting in shrinking of
electron cloud.
• Number of protons are more than number of electrons.
• Nucleus exerts greater attraction force on the remaining electrons.
• Hence, the ionic radius of cation decrease.

Trends in the ionic radius: negative ions

 The ionic radii of negative ions (anions) are greater than their corresponding
atomic radii.
 This is because the number of protons are less than number of electrons.
 When one or more electrons are added to the outer shell of an atom forming a
negative ion, there is an increase in the repulsion between the negatively
charged clouds.
 Hence, the ionic radius of anion increase.

FIRST IONISATION ENERGY

Definition
The energy required to remove ONE MOLE of electrons (to infinity) from ONE MOLE
of gaseous atoms to form ONE MOLE of gaseous unipositive ions.
+ -
e.g. Na(g) Na (g) + e

Make sure you write in the (g)

+ -
Al(g) Al (g) + e

It is a measure of the energy required to remove an outer shell electron from a gaseous
atom. Electrons are negatively charged and are attracted to the positively charged
nucleus. Electrons that are held more strongly will require more energy to overcome
the attraction.
1st Ionisation Energy INCREASES across a period
Nuclear charge increases by one each time. Each extra electron, however, is going
into the same main energy level so is subject to similar shielding and is a similar

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distance away from the nucleus. Electrons are held more strongly and are harder to
remove. However the trend is not consistent.

6
 Li Na K Rb Cs.

Down Group 1, conductivity decreases due to lower charge density as the atom gets
bigger.

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Ceramic:

The term ceramic generally applies to any class of inorganic, non-metallic

product subjected to high temperature during manufacture or use.
This deals with the properties of some ceramic materials, and talks about the
physical properties of ceramics in terms of their structures.

The structures

Ceramics have giant structures of one type or another, with strong bonds between
the atoms (or ions) which make them up.

The physical properties

Strength

The strong bonds holding the atoms (or ions) together in three dimensions will make
the ceramic hard and strong, but also brittle.

Example. The floor tile is obviously hard, and you can stand on a floor tile, or place
heavy furniture on it without it breaking - so it is strong. On the other hand, it isn't
difficult to break a tile in half by snapping it, especially if you score a shallow line on it
first with a cutting tool - it is brittle.

Melting points

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Ceramics have high melting points because of the need to break the strong covalent
or ionic bonds holding the giant structure together. It takes a very high temperature
to do this.

Electrical conductivity

Most ceramics are good electrical insulators. If they are covalent, there are no free
electrons to move around. If they are ionic, the ions aren't free to move in the solid.

This deals with the uses of modern ceramic materials involving magnesium oxide,
aluminium oxide and silicon(IV) oxide, and the relationship with their structures.

Magnesium oxide

Ceramics made from magnesium oxide are used in:

 furnace linings (refractory bricks), because the ceramic has a high melting
point (strong forces in the giant structure);
 heating elements (for example for electric cookers), because the ceramic is
good electrical insulator (no free electrons, and the ions aren't free to move in
the solid).

Aluminium oxide

Various web sources describe this as the most important oxide ceramic.

Uses of aluminium oxide ceramics include:

 high temperature and high voltage electrical insulators, because the ceramic
has a high melting point and is a good electrical insulator (strong attractions in
the giant structure; no free electrons, and the ions aren't free to move either);
 replacement hip joints. Hip joints are a ball and socket arrangement, and the
ball or socket can both be made of aluminium oxide ceramic material. The
strong forces holding the aluminium and oxide ions together make it very
resistant to wear. Aluminium oxide is also chemically resistant because of the
large amount of energy needed to separate the ions.

Silicon(IV) oxide (silicon dioxide)

Uses of silicon dioxide ceramics include:

 as furnace linings (refractory bricks) in furnaces for the production of glass,

because the giant covalent structure has a very high melting point due to the
strength of the Si-O covalent bonds in three dimensions;
 to make ceramic tiles to protect the space shuttle. The tiles are light, and have
a high melting point.

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 REACTIONS OF PERIOD 3 ELEMENTS WITH OXYGEN

Sodium: Reacts vigorously with oxygen. Burns with a yellow flame.

4Na(s) + O (g)  2Na O(s) (white solid)
2 2
Magnesium: Burns vigorously when heated with oxygen. Burns with a bright white flame.
2Mg (s) + O (g)  2MgO (s)
2
Aluminum: Burn vigorously with a white flame
4Al(s) + 3O (g)  2Al O (s)
2 2 3
Silicon: Reacts slowly with oxygen
Si(s) + O (g) SiO (s)
2 2
Phosphorus: Burns vigorously with oxygen with an yellow or white flame
4P(s) + 5O (g)  P O (s)
2 4 10
Sulfur: Burns gently with a brilliant blue flame.
S(s) + O (g)  SO (g)
2 2
Further oxidation to sulfur trioxide.
2SO (g) + O (g) 2SO (g)
2 2 3
Chlorine and argon: do not react directly with oxygen.

REACTIONS OF PERIOD 3 ELEMENTS WITH CHLORINE

Sodium: Reacts vigorously with chlorine gas.

2Na(s) + Cl (g)  2NaCl(s)
2
Magnesium: Reacts vigorously with chlorine gas.
Mg (s) + Cl (g)  MgCl (s)
2 2
Aluminum: Reacts vigorously with chlorine gas.
2Al(s) + 3Cl (g)  Al Cl (s)
2 2 6
Silicon: Reacts slowly with chlorine
Si(s) + 2Cl (g) SiCl (l)
2 4
Phosphorus:
P (s) + 6Cl (g)  4PCl (l)
4 2 3
Reacts slowly with excess chlorine gas
2P(s) + 5Cl (g)  2PCl (s)
2 5
Sulfur: forms chlorides, such as SCl and S Cl
2 2 2
Argon: does not form chloride.

15
Dimer of aluminium chloride

16
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Phosphorus(V) Oxide

Phosphorus(III) Oxide

21
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pH of the oxides’ aqueous solutions.

Sodium Oxide Magnesium Aluminium Phosphorus(V) Sulphur dioxide

oxide Oxide oxide
14 9 7 2-4 3
SiO2 is insoluble in water. Its pH can be considered to be 7.

Summary of Period 3 oxides:

• Metal oxide (on the left of the Periodic Table) have giant ionic lattice structure with
ionic bonding and react with water to give alkalis. They are basic oxide and react with
acids to give salts.
• Non-metal oxides (on the right of Periodic Table) have simple molecular structure
with covalent bonding and react with water to give acids. They are acidic oxides and
react with bases to give salts.
• Oxides in the centre of Periodic Table have intermediate properties. They are
amphoteric oxide and react with both acids and bases.

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25
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(Gp 1) NaCl(s) + aq ==> Na+(aq) + Cl- (Gp 2) MgCl2(s) + aq ==> Mg2+(aq) + 2Cl-
(aq) just dissolves, ~pH 7 (aq) just dissolves, ~pH 7

(Gp 3) AlCl3(s) +
3H2O(l) ==> Al(OH)3(s) +
3HCl(g) with limited water you get
hydrolysis to give acid fumes (Gp 4) SiCl4(l) + 2H2O(l) ==> SiO2(s) +
4HCl(aq) hydrolysis to give strongly acid
3+
AlCl3(s) + aq ==> Al (aq) + 3Cl - solution
(aq) excess water, weakly acidic
solution due to the acidity of
[Al(H2O)6]3+
(Gp 5) PCl3(l) + 3H2O(l) ==>
H3PO3(aq) + 3HCl(aq) hydrolysis to (Gp 6) S2Cl2(g) + H2O(l) ==> HCl(aq), S(s),
give weakly acid solution SO2(aq),
H2SO3(aq), H2SO4(aq), H2S(aq) - complex
PCl5(s) + 4H2O(l) ==> H3PO4(aq) + redox/hydrolysis reaction but final
5HCl(aq) hydrolysis to give solution is quite acidic
strongly acid solution
(Gp 7) chlorine itself Gp 0 argon has no chloride

• Metal chlorides (on the left of the Periodic Table) have giant ionic lattice structures
with ionic bonding and dissolve with water to give neutral (or slightly acidic)
solutions. They are neutral chloride.
• Non-metal chlorides (on the right of Periodic Table) have simple molecular structures
with covalent bonding and react with water to give acids. They are acidic chlorides.

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Group 2 elements

29
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Melting point depends on:
1) the strength of the bonds.
2) the structure of the element ( closely packed or loosely packed)

Although the metallic bond in magnesium is stronger than calcium, the magnesium atoms
are loosely packed compared to the calcium. Hence less energy is needed to break the
metallic bond in magnesium and therefore has lower melting point than calcium.

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34
A flame test uses a piece of nichrome wire. Dip the end of the wire in concentrated
hydrochloric acid and then hold it in a hot bunsen flame. If the wire is not contaminated,
the colour of the flame will not change.

If the flame changes colour, dip the wire in concentrated hydrochloric acid again and return it
to the Bunsen flame. Repeat this procedure until the wire shows no change of colour in
the flame.

Now dip the end of the wire in concentrated hydrochloric acid and put the wire into
the solid which you are using for the flame test. A small amount of the metal chloride will
form on the wire. Hold the wire in the flame and see what colour is produced. The table below
shows which colours are produced by some metal ions.

Metal Ion Flame Colour

+
Lithium Li Dull Red
Sodium Na+ Yellow/Orange
Potassium K+ Lilac (violet)
2+
Calcium Ca Brick Red
Barium Ba2+ Apple Green
Copper Bluish green
Strontium Blood red

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It is found that the chemistry of a first-row (2nd Period) element often has similarities to the
chemistry of the second-row (3rd Period) element one row to the right of it in the Periodic
Table. Thus (get your Periodic Table out!) the chemistry of Li has similarities to that of Mg,
the chemistry of Be has similarities to the chemistry of Al, and the chemistry of B has
similarities to the chemistry of Si, These are called diagonal relationships (it is not as noticeable
after B/Si).

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Uses: Ca(OH)2 used in agriculture to neutralise acid soils
+ 2+
Ca(OH)2(s) + 2H (aq) —> Ca (aq) + 2H2O(l)
Mg(OH)2 used in toothpaste and indigestion tablets as an antacid
(An antacid is a substance which neutralizes stomach acidity).
+ 2+
Mg(OH)2(s) + 2H (aq) —> Mg (aq) + 2H2O(l)
Both the above are weak alkalis and not as caustic (the property of a substance that causes
corrosion) as sodium hydroxide.

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The metal nitrates and carbonates become more thermally stable going down the group.

This means that Magnesium compounds are least stable to heat (lower temperatures can
decompose them) while Barium compounds are most stable to heat (do not decompose easily
and require a higher temperature to decompose)

This is because down the group charge density decreases. Therefore polarizing power also
decreases down the group. It becomes less likely for the anion to be distorted.

Polarisation or distortion of the anion charge cloud would cause the anion to break down
forming a smaller electron cloud that is less polarizing and more stable.

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Major Uses of Group II compounds

Magnesium - burns with a dazzling white light. So it is used to make light flares, incendiary
bombs. Magnesium is high in the reactivity series and hence it is used as sacrificial metal to
protect steel from corrosion on ships’ hull. It is also used to extract Titanium.

Magnesium Oxide – Neutralises excess acidity in the stomach. It can be made into MgO
ceramic which has a v high melting point. Therefore used to line kilns and furnaces.

Magnesium hydroxide – Weak alkali, used in antacids to neutralize acidity of stomach juices.
Also found in toothpaste.

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 i) trend in solubility of sulfates

The solubility of the sulfates decreases down group II.

MgSO4 is soluble, CaSO4 is sparingly soluble and SrSO4 and BaSO4 are insoluble.

If sulphuric acid or sodium sulphate is added to aqueous solutions of calcium, strontium or

barium ions, a white precipitate will be formed:
Ba2+(aq) + SO42-(aq)  BaSO4(s) thick white precipitate formed
Sr2+(aq) + SO42-(aq)  SrSO4(s) thick white precipitate formed
Ca2+(aq) + SO42-(aq)  CaSO4(s) faint white precipitate formed

If dilute sulphuric acid or sodium sulphate is added to a solution of Mg2+ or Be2+, there is no
reaction and no precipitate is formed.

The thick white precipitate formed when barium ions are added to sulfate ions can be used as
a test for sulfate ions:
- add 1 cm3 of aqueous barium chloride, and also1 cm3 of dilute hydrochloric acid,
to 1 cm3 of the unknown solution. If a thick white precipitate is formed, and that
precipitate does not dissolve in dilute HCl, then sulphate or hydrogensulphate ions
are present.

The hydrochloric acid removes any other ions such as carbonate or hydroxide ions which
may affect the test.

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 Group 17

GENERAL • non-metals
• exist as separate diatomic molecules… eg Cl2
2 5
• all have the electronic configuration ... ns np
TRENDS • appearance
• boiling point
• electronic configuration
• electronegativity
• atomic size
• ionic size
• oxidising power

Electronic Configuration.
Fluorine Chlorine Bromine Iodine
Atomic Number 9 17 35 53
Old configuration 2.7 2.8.7 2.8.18.7 2.8.18.18.7
New configuration 1s2 2s2 2p5 …. 3s2 3p5 …. 4s2 4p5 …. 5s2 5p5

Electrons go into shells further from the nucleus.

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Electronegativity:

F Cl Br I
Electronegativity 4.0 3.0 2.8 2.5
Electronegativity decreases down the Group.

 The increasing nuclear charge due to the greater number of protons should attract the
electrons more, but there is an
 Increasing number of shells, which means more shielding and less pull on the
electrons
 Increasing atomic radius which means attraction drops off as distance increases.

OXIDISING POWER:

• halogens are oxidising agents

• they need one electron to complete their octet
• the oxidising power gets weaker down the group
• the trend can be explained by considering the nucleus’s attraction for the incoming electron
which is affected by the...
• increasing nuclear charge which should attract electrons more

but this is offset by • INCREASED SHIELDING

• INCREASING ATOMIC RADIUS
This is demonstrated by reacting the halogens with other halide ions.

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HALOGENS - DISPLACEMENT REACTIONS:

THE DECREASE IN REACTIVITY DOWN THE GROUP IS DEMONSTRATED USING

DISPLACEMENT REACTIONS...
A SOLUTION OF THE HALOGEN IS ADDED TO A SOLUTION OF A HALIDE

HALIDES ARE SALTS FORMED FROM HALOGENS

A MORE REACTIVE HALOGEN WILL DISPLACE A LESS REACTIVE ONE
e.g. CHLORINE + SODIUM BROMIDE BROMINE + SODIUM
CHLORIDE
Cl2(aq) + 2NaBr(aq) ——> Br2(aq) + 2NaCl(aq)
Cl2(aq) + 2Br¯(aq) ——> Br2(aq) + 2Cl¯(aq)

CHLORINE + SODIUM IODIDE IODINE + SODIUM CHLORIDE

BROMINE + SODIUM IODIDE IODINE + SODIUM BROMIDE
BUT BROMINE + SODIUM CHLORIDE No reaction
(Bromine is below chlorine in the Group so is less reactive)

OXIDISING POWER:
Chlorine oxidises bromide ions to bromine
Cl2 + 2Br¯ ——> Br2 + 2Cl¯
Chlorine oxidises iodide ions to iodine
Cl2 + 2I¯ ——> I2 + 2Cl¯
Bromine oxidises iodide ions to iodine
Br2 + 2I¯ ——> I2 + 2Br¯
Displacement reactions – Experiment.

Sodium Chloride Sodium Bromide Sodium Iodide

Chlorine Solution stays Solution goes from Solution goes from
colourless colourless to orange- colourless to brown
NO REACTION reddish brown colour solution-black ppt.
BROMINE IODINE FORMED
FORMED

Bromine Solution goes from Solution goes from Solution goes from
colourless to orange- colourless to orange- orange reddish
reddish brown. NO reddish brown brown to black ppt.
REACTION colour. IODINE FORMED
NO REACTION

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OTHER REACTIONS OF CHLORINE:
Water Halogens react with decreasing vigour down the group as their oxidising
power decreases
Litmus will be turned red then decolourised in chlorine water

0 -1 +1
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)
strong acid bleaches by oxidation
This is an example of DISPROPORTIONATION …‘simultaneous oxidation and reduction of
a species’
Alkalis Chlorine reacts with cold, aqueous sodium hydroxide. (15o C)

2NaOH(aq) + Cl (g) —> NaCl(aq) + NaOCl(aq) + H O(l)

2 2
Sodium Chlorate(I)
o
Chlorine reacts with hot, aqueous sodium hydroxide. (70 C)

6NaOH(aq) + 3Cl2(aq) —> 5NaCl(aq) + NaClO3(aq) + 3H2O(l)

Sodium Chlorate(V)

TESTING FOR HALIDE IONS using AgNO

3
• make a solution of the halide
• acidify with dilute nitric acid – this prevents the precipitation of other salts
• add a few drops of silver nitrate solution
• treat any precipitate with dilute ammonia solution
• if a precipitate still exists, add concentrated ammonia solution
Note: Adding ammonia or concentrated ammonia is to verify the result as in these precipitates
are similar in colour.

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 + +
halides precipitate as follows Ag (aq) + X¯(aq) ——> Ag X¯(s)
+
when they dissolve in ammonia a colourless diammine complex is formed [Ag(NH3)2] (aq)

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TESTING FOR HALIDES – Conc. H SO
2 4
• an alternative test for halides
• add concentrated sulphuric acid carefully to a solid halide
• H2SO4 displaces the weaker acids HCl, HBr, and HI from their salts
• as the hydrogen halides become more powerful reducing agents down the group they can
react further by reducing the sulphuric acid to lower oxidation states of sulphur
- - -
• Compounds that contain Cl , Br or I ion will react with concentrated sulfuric
acid.
• All of these reactions produce one or more poisonous gases.
• Hydrogen chloride gas can be prepared by dropping concentrated sulfuric acid
slowly onto the appropriate sodium salt.

NaCl (s) + H SO (l)  NaHSO (s) + HCl (g)

2 4 4
Sodium hydrogen sulfate
•The HCl produced is visible as white fumes.
•However, we can’t use the same reaction to prepare samples of pure hydrogen
bromide or hydrogen iodide.
• Concentrated sulfuric acid is a relatively strong oxidising agent.
• HCl, HBr and HI are reducing agents. HCl is a weak Reducing agent but HBr and HI
are stronger reducing agents. They can reduce sulphuric acid to sulphur dioxide or
Sulphur or even hydrogen sulphide.
• HBr and HI formed in the reaction between sodium bromide or sodium iodide, and
concentrated sulfuric acid undergoes further reaction.

With sodium bromide, the sulfuric acid is reduced to sulfur dioxide gas by hydrogen
bromide:

NaBr(s) + H2SO4 (l)  NaHSO4 (s) + HBr (g)

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Followed by oxidation of HBr(g):

2 HBr (g) + H2SO4 (l)  Br2 (g) + SO2 (g) + 2H2O (l)

Reddish brown

With sodium iodide, the sulfuric acid is reduced to sulfur dioxide, sulfur and hydrogen
sulfide:
Nal (s) + H SO (l)  NaHSO (s) + Hl (g)
2 4 4
Followed by oxidation of HI (g):
2Hl (g) + H SO (l)  I (g) + SO (g) + 2H O (l)
2 4 2 2 2
violet/ purple vapour
And:
6Hl (g) + H SO (l)  3I (g) + S (s) + 4H O (l)
2 4 2 2
yellow solid
And:
8Hl (g) + H SO (l)  4I (g) + H S (g) + 4H O (l)
2 4 2 2 2
hydrogen sulphide (smell of bad eggs)
• The hydrogen chloride is not a strong reducing agent, thus hydrogen chloride
does not reduce the sulphuric acid to sulphur dioxide.
• The hydrogen bromide produced reduces the sulphuric acid to sulphur dioxide
• The hydrogen iodide is a stronger reducing agent than hydrogen bromide and
reduces concentrated sulphuric acid to hydrogen sulphide and sulphur.

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HYDROGEN HALIDES – PROPERTIES:
Boiling points: At room temperature and pressure HCl, HBr, HI are colourless gases,
HF is a colourless liquid.
b. pts ... HF 20°C HCl -85°C HBr -69°C HI -35°C

HF’s boiling point is higher than expected due to hydrogen bonding

Reducing ability: Increases down the group as bond strength decreases

-1
bond energy H-F 568 H-Cl 432 H-Br 366 H-I 298 / kJ mol

Smallest bond length Longest bond length

HI is oxidized to I2 most easily.

HALOGENS & HALIDES – USES:

Chlorine, Cl2 • water purification
• bleach
• solvents
• polymers - poly(chloroethene) or PVC, Poly vinyl chloride.
• CFC’s – chloro fluoro carbons

Fluorine, F2 • CFC’s
• polymers - PTFE poly(tetrafluoroethene) as used in non-stick frying pans,
electrical insulation, waterproof clothing
Fluoride, F¯ • helps prevent tooth decay

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 - tin fluoride is added to toothpaste
- sodium fluoride is added to water supplies

Hydrogen fluoride, HF(aq) • used to etch glass

Silver bromide, AgBr • used in photographic film
Chlorination of water
• Adding a small amount of chlorine to a water supply will kill bacteria and make
the water safer to drink. The chlorine undergoes disproportionation in water:
Cl (aq) + H O(l)  HCl + HClO(aq)
2 2

Ox. no. of Cl 0 -1 +1
• HClO is called chloric(I) acid. It decomposes slowly in solution, producing
reactive oxygen atoms that kill bacteria in water:
HClO  HCl + O
Bleach
o Bleach is an equal mixture of sodium chloride (NaCl) and sodium chlorate(I)
(NaClO), made from chlorine and cold alkali.
o It ‘bleaches’ colour and stains because oxygen atoms from the chlorate(I) ion
oxidise dye and other coloured molecule.
o They also kill bacteria when toilets are cleaned with bleach
 The halogens are found in many organic compounds such as the plastic PVC
(poly(chroethene) or polyvinyl chloride) and halogenated hydrocarbons used as
solvents, refrigerants and in aerosols.

Nitrogen and its compounds.

Nitrogen :
• occurs in Group XV
2 2 3
• electronic configuration ... 1s 2s 2p
• exists as a diatomic molecule N
2
• very unreactive - triple bond between atoms has a high bond dissociation enthalpy
• makes up 79% of atmospheric gases
Oxidation states :
Exhibits the whole range of oxidation states
+5 HNO NO ¯ oxidising agent
3 3

+4 NO
2

+3 HNO NO ¯
2 2

+2 NO
+1 NO
2

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0 N
2

-1 NH OH Hydroxylamine
2

-2 NH
2 4
+
-3 NH NH reducing agent
3 4

Ammonia
• covalent hydride of nitrogen
• higher than expected boiling point due to intermolecular hydrogen bonding
• pyramidal in shape due to repulsion between 3 bond pairs and 1 lone pair

• Acts as Lewis base due to lone pair on nitrogen

• Acts as a Bronsted-Lowry base as it can pick up protons.
+ +
NH + H  NH
3 4

Ammonium ion:
• ammonia can use its lone pair to form a co-ordinate (dative covalent) bond to a proton

Ammonium salts :
• formed when ammonia reacts with acids
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 NH + HCl  NH Cl (ammonium chloride)
3 4

2NH + H SO  (NH ) SO (ammonium sulfate)

3 2 4 4 2 4

NH + HNO  NH NO (ammonium nitrate)

3 3 4 3

• ammonia is displaced from its salts by treating them with a stronger base
NaOH + NH Cl  NH + NaCl + H O
4 3 2

OR
Ca(OH) + NH Cl(s)  NH (g) + CaCl + H O(l)
2 4 3 2 2

Question: Which of the reagent when mixed and heated with ammonium sulphate liberates
ammonia?

A. Aqueous Bromine
B. Dilute Hydrochloric acid
C. Limewater
D. Acidified potassium dichromate(VI)

Haber Process:

• Ammonia is prepared industrially by the Haber Process

-1
N (g) + 3H (g) 2NH (g) : ∆H = -92 kJ mol
2 2 3

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Typical conditions
Pressure: 200 atmospheres
Temperature: 400-600°C
Catalyst: iron
Equilibrium theory favours
1. low temperatures as it is an exothermic reaction - and so higher yield obtained at lower
temperature.
2. high pressure as there is a decrease in number of gaseous molecules.
Kinetic theory favours
1. high temperature as it provides greater average energy + more frequent collisions
2. high pressure as there will be more frequent collisions for gaseous molecules
3. catalyst that will lower activation energy.

Compromise conditions
Which is better?
A low yield in a shorter time (if temperature is high) or
A high yield over a longer period (if temperature is low).
The conditions used are a compromise with the catalyst enabling the rate to be kept up, even
at a lower temperature.

Industrial importance of ammonia and nitrogen compounds derived from ammonia:

ammonia can be converted to nitric acid

4NH (g) + 5O (g)  NO (g) + 6H O (l)
3 2 2

2NO(g) + O (g) 2NO (g)

2 2

4NO (g) + O (g) + 2H O (l)  4HNO (l)

2 2 2 3
nitric acid is used to make fertilisers, dyes, polyamide polymer (NYLON) and explosives

Fertilizers :
• nitrates encourage leaf and grass growth
• 80% of the ammonia produced is made into fertilisers such as ammonium nitrate
(NITREAM) and ammonium sulphate.
NH + HNO  NH NO
3 3 4 3

2NH + H SO  (NH ) SO
3 2 4 4 2 4
• water supplies can become contaminated by fertilizers

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 • nitrates encourage algae growth which leads to de-oxygenation of streams and
reduction in wildlife – eutrophication.

• A bloom of algae can spread across the surface, blocking out the light for other
plant life in the water.
• When the plants and algae die, bacteria in the water feed on them, decomposing
the plant material.
• The bacteria multiply rapidly with so much food available, using up the
dissolved oxygen in the water.
• Fish extract dissolved oxygen from water taken in through their gills. Without
oxygen they die, affecting the whole ecosystem.

Occurrence, and catalytic removal, of oxides of nitrogen:

Nitrogen oxides NO
x
• Nitrogen forms several oxides, including
- NO nitric oxide
- N O nitrous oxide - ‘laughing gas’ (use as anaesthetic)
2

- NO nitrogen dioxide (Brown)

2
• mainly formed during the burning of fossil fuels
• high temperature processes allow nitrogen to combine with oxygen
• nitrogen oxides encourage photochemical smog and breathing problems
• major pollutants from car exhausts
• removed using catalytic converters
(note: photochemical smog is caused by light reacting with the pollutant molecule)

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Catalytic converters
In the catalytic converter ... CO is converted to CO
2
• NO are converted to N
x 2
• unburnt hydrocarbons to CO and H O
2 2
• e.g. 2NO + 2CO  N + 2CO
2 2
• catalysts are made of finely divided rare metals such as palladium, rhodium,
platinum
• leaded petrol must not pass through the catalyst as the lead deposits on the
catalyst’s surface and “poisons” it, thus blocking sites for reactions to take
place.

Role of sulfur dioxide in the formation of acid rain:

Origin
• Rain has always been acidic due to the presence of carbon dioxide, nitrogen
oxides and sulfur dioxide from natural sources. Rain falling from an unpolluted
atmosphere would have a pH of about 5.5 to 6.0. However, in industrial areas,
rain has a significantly lower pH, as low as 4.0 due to polluted atmosphere.
Such rain is called acid rain.
Main source
• sulfur dioxide and oxides of nitrogen
• Nitrogen oxides catalyses the oxidation of sulphur dioxide to sulfur (VI) oxide.
SO (g) + NO (g) ——> SO (g) + NO (g)
2 2 3

NO (g) + ½O (g) ——> NO (g)

2 2

overall SO (g) + ½O (g) ——> SO (g)

2 2 3
• Sulfur (VI) oxide dissolves in water to produce a strong acid (sulfuric acid)
SO (g) + H O (l) ——> H SO (l)
3 2 2 4
• Nitrogen (IV) oxide dissolves with oxygen in water to form nitric acid
2NO (g) + H O (l) + ½O (g) ——> 2 HNO (l)
2 2 2 3

Note: NO, or nitric oxide, is a colourless gas produced when nitrogen and oxygen combine at
high temperature. On contact with air it is converted to nitrogen dioxide. Sulfur dioxide
at high temperatures can oxidise to form sulfur trioxide.
Effect of acid rain
• erosion of rocks
• damage to limestone and marble buildings
• increasing acidity in rivers and lakes
• de-forestation
• Corrosion of metal e.g. Iron and steel
To Minimise the effect of acid rain:

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 • Remove sulfur dioxide from the exhaust gasses of power stations where fossil
fuels particularly coal, are burned. SO2 can be removed by passing it through
calcium oxide or calcium carbonate.

Equation:
2CaO(s) + SO (g)  CaSO (s) calcium sulfite
2 3

2CaO(s) + 2SO (g) + O (g) 2 CaSO (s)

2 2 4

CaCO (s) + SO (g)  CaSO (aq) + CO (g)

3 2 3 2

2CaO(s) + H O(l)  Ca(OH) (aq)

2 2

Ca(OH) (aq) + SO (g)  CaSO (aq) + H O(l)

2 2 3 2
• Remove sulfur from petrol and diesel fuel at the oil refinery.
• Use catalytic converters on car exhausts system, reducing the emissions of
oxides of nitrogen and hence the formation of sulfur trioxide by the catalytic
cycle seen earlier.

General properties of sulfur dioxide

• simple covalent molecule
• angular in shape - repulsion between 1 lone pair and 2 double bond pairs
• sulphur is in oxidation state +4
• reducing agent
• dissolves in water to produce a weak acidic solution
• Sulfur dioxide dissolves well in water, forming sulfuric (IV) acid (H SO , also
2 3
knows as sulfurous acid). Sulfuric (IV) acid is in equilibrium with
- 2-
hydrogensulfite ions, HSO3 , and sulfite ions, SO :
3
+ - + 2-
• H SO ⇌ H + HSO ⇌ 2H + SO
2 3 3 3
The industrial importance of sulfuric acid

• making fertilisers
• making detergents
• paper industry
• electrolysis / car batteries
• making paints
• making dyestuff
• pigments
• synthetic fibers
• plastics
• cleaning leather
• cleaning metal surfaces (‘pickling’)

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