Oxides, Chlorides and

Hydrides

CHEMISTRY 2 - A (K17AE)
Oxides
across a period 2 & 3 - the oxides change
Melting points- from very high melting point solids
to low melting point solids, liquids or gases

Bonding - from ionic to covalent

Structure - they change from ionic lattices to covalent molecules

CHEMISTRY 2 - A (K17AE)
 Melting points of period 2 & 3
oxides
3000 Series 1
Series 2

2500
M
e
l
t 2000
i
n
g
1500 Period 2
p
o
i 1000
n
Period 3
t

( 500
o
C
)
0

1 2 3 4 5 7
6
-500
Group

CHEMISTRY 2 - A (K17AE)
 Types of bonding in oxides
Li Be B C N O F

Na Mg Al Si P S Cl

ionic lattice

ionic/covalent network

covalent network

covalent molecular
Electrical conductivity

Melts or solutions of ionic oxides

CHEMISTRY 2 - A (K17AE)
‘Reaction’ of oxides with water

Li Be B C N O F

Na Mg Al Si P S Cl

forms an alkali e.g. Na2O(s) + H2O (l) NaOH(aq)

forms a weak alkali

no reaction/insoluble

forms an acid e.g. NO2 (s) + H2O (l) H NO3(aq)

slightly soluble but no reaction

CHEMISTRY 2 - A (K17AE)
 Acid/base character of oxides
Li Be B C N O F

Na Mg Al Si P S Cl

basic

weakly basic Al2O3 + 6HCl 2AlCl3 + 3H2O

amphoteric
Al2O3 + 3H2O + NaOH 2NaAl(OH)4
acidic

neutral

CHEMISTRY 2 - A (K17AE)
Chlorides - States

Shown above are the chlorides of the Period 3 elements Na  Cl

NaCl, MgCl2 and AlCl3 are all solids, typical of ionic networks
SiCl4, PCl3 and S2Cl2 are all liquids, typical of covalent molecules

ClCl i.e.Cl2 is a gas, typical of covalent molecules

CHEMISTRY 2 - A (K17AE)
Types of bonding in chlorides
Li Be B C N O F

Na Mg Al Si P S Cl

ionic lattice

partially covalent network

covalent molecular

Electrical conductivity
melts or solutions of ionic chlorides
Chlorides - Intermediate Bonding

AlCl3 exists as highly polar covalent molecules, Al2Cl6 dimers, at

room temperature; AlCl3 when vapourised. Coordinate covalent
bonds are used to form ‘chlorine bridges’ in the dimer form.

When a voltage is applied, AlCl3 ionises to form Al3+ ions and Cl-
ions and is able to conduct like an ionic compound.
CHEMISTRY 2 - A (K17AE)
‘Reaction’ of chlorides with water
Li Be B C N O F

Na Mg Al Si P S Cl

soluble

insoluble/immiscible

produces fumes of hydrogen chloride

e.g. PCl5 (s) + 4H2O (l) H3PO4(aq) + 5HCl (aq)

Acid/base character of chlorides
Li Be B C N O F

Na Mg Al Si P S Cl

weakly acidic

acidic

neutral
Hydrides
H- ion very strong base/reducing agent e.g.
2KH(s) + 2H2O(l) H2(g) + 2KOH(aq)

Reaction with sodium hydride produces the metal from

many metal oxides e.g.
CuO + NaH Cu + NaOH

Lithium aluminium hydride (LiAlH4) and sodium tetrahydroborate (NaBH4)

used in organic chemistry when strong reducing agents required
 Types of bonding in hydrides
ionic lattice

ionic/covalent

polymeric

covalent molecular
Li Be B C N O F

Na Mg Al Si P S Cl

good non-conductors poor Electrical conductivity

when molten
‘Reaction’ of hydrides with
water
Li Be B C N O F

Na Mg Al Si P S Cl

forms hydroxide and hydrogen

insoluble

soluble

forms hydroxide
Acid/base character of hydrides
Li Be B C N O F

Na Mg Al Si P S Cl

strongly alkaline

alkaline

weakly alkaline

neutral

weakly acidic

strongly acidic
Amphoteric Oxides
Amphoteric oxides are formed by elements lying
between the metals and non-metals in the Periodic Table.

Increasing oxide acidity

acidic oxides
basic oxides
amphoteric oxides

Increasing oxide acidity

CHEMISTRY 2 - A (K17AE)
Transition Metals - Definition 1
The easiest, but least useful, definition of a Transition
metal is that it is found in the d-block of the table.

CHEMISTRY 2 - A (K17AE)
Transition Metals - Definition 2
Another definition of a Transition metal is that it has
an incomplete d subshell. This excludes Cu and Zn.
Atomic No. Symbol 4s 3d Configuration

NB 4s is of lower energy so fills before 3d. Cr and Cu are exceptions to Aufbau rule
CHEMISTRY 2 - A (K17AE)
Filling of d-orbitals - exceptions
Cu and Cr are exceptions to the Aufbau principle.
Cr should be:

Cr actually is:
There is a special stability associated with all the d-orbitals being
half-filled.

Cu should be:

Cu actually is:
There is a special stability associated with all the d-orbitals being
completely filled
CHEMISTRY 2 - A (K17AE)
Transition Metals - Definition 3
Another definition of a Transition metal is that it has at
least one ion with an incomplete d subshell.
NB 4s is now at higher energy so empties before 3d.
Atomic No. Symbol 4s 3d
3+
Sc only forms a Sc3+ ion so
3+
would be excluded by this
4+
definition.
3+
2+
2+
2+
2+ Zn only forms a Zn2+ ion so
2+ would be also be excluded
2+ by this definition.
CHEMISTRY 2 - A (K17AE)
CHEMISTRY 2 - A (K17AE) 21
Transition Metals - Best Definition
There are 3 main characteristics of a Transition metal

* they can produce ions with different valencies

Sc & Zn produce only one possible ion each
* they produce coloured compounds
Sc & Zn have no coloured compounds
* they can act as catalysts
Sc & Zn have no catalytic applications

Therefore, the best definition of a Transition metal is that it has at

least one ion with an incomplete d subshell.

CHEMISTRY 2 - A (K17AE)
Oxidation States
Transition metals exhibit variable oxidation states
of differing stability.

Transition metals exhibit variable oxidation states because they can

not only lose their 4s electrons but some or all of their 3d electrons.
CHEMISTRY 2 - A (K17AE)
Oxidation States - stability 1
Sometimes electron configurations can be used to
explain why one oxidation state is more stable.

For example, during rusting Fe2+ ions are formed first, but
they then change into Fe3+ ions.

2+

3+

The Fe3+ ion forms in preference to Fe2+ because of the extra stability
associated with all the d-orbitals being half-filled.

CHEMISTRY 2 - A (K17AE)
Oxidation States - stability 2
Sometimes electron configurations cannot be used
to explain why one oxidation state is more stable.

For example, copper forms two ions Cu+ and Cu2+. Most
copper compounds contain the soluble Cu2+ ion.

1+

2+

The Cu+ ion should form in preference to Cu2+ because of the extra
stability associated with all the d-orbitals being filled.

In fact the Cu2+ ion usually forms in preference to Cu+ because there
is even more extra stability due to forming in solution.
CHEMISTRY 2 - A (K17AE)
Oxidation Numbers
Oxidation numbers are a way of keeping track of
electrons. They do not necessarily represent the ‘true’
charge on a particle but they work!

Rule 1 Simple ions such as Na+, K+, Cl— etc continue to

count as + 1 or - 1 .
Rule 2 Oxygen is always assumed to be - 2 .
Rule 3 Hydrogen is always assumed to be +1 .
Rule 4 Overall charge on a compound is always 0 .

Rule 5 In polyatomic ions, the sum of all the oxidation

numbers is equal to the overall charge on the ion.
CHEMISTRY 2 - A (K17AE)
Oxidation Numbers - example 1
What is the oxidation number for Mn in KMnO4 ?

Rule 1 We assume K counts as + 1

Rule 4 Overall the compound is 0, so MnO4 must be -1.
Rule 2 We assume each oxygen is -2, so 4 x O = - 8

Rule 5 Overall charge on ion is -1, so Mn must be +7 .

When permanganate reacts to form Mn2+ ions we can calculate

that 5e must be gained;
Mn7+ + 5e  Mn2+
Alternatively,
MnO4- + 8H+ + 5e  Mn2+ + 4H2O
CHEMISTRY 2 - A (K17AE)
Oxidation Numbers - example 2
What is the oxidation number for S in SO42- ?
Rule 2. We assume each oxygen is -2, so 4 x O = - 8
Rule 5. Overall charge on ion is -2, so S must be +6 .
What is the oxidation number for S in SO32- ?
Rule 2. We assume each oxygen is -2, so 3 x O = - 6
Rule 5. Overall charge on ion is -2, so S must be +4 .

When sulphite ions react to form sulphate ions we can calculate

that 2e must be lost;
S4+  S6+ + 2e
Alternatively,
SO32- + H2O  SO42- + 2H+ + 2e
CHEMISTRY 2 - A (K17AE)
Oxidation Numbers - example 3
What is the oxidation number for Cr in CrO42- ?
Rule 2. We assume each oxygen is -2, so 4 x O = - 8
Rule 5. Overall charge on ion is -2, so Cr must be +6 .
What is the oxidation number for Cr in Cr2O72- ?
Rule 2. We assume each oxygen is -2, so 7 x O = - 14
Rule 5. Overall charge on ion is -2, so 2 x Cr must be +12
so Cr must be +6
When chromate ions react to form dichromate ions we can
calculate that no electrons are gained or lost.
Alternatively,
2CrO42- + 2H+  Cr2O72- + H2O
CHEMISTRY 2 - A (K17AE)
CHEMISTRY 2 - A (K17AE)
CHEMISTRY 2 - A (K17AE)