PHYSICAL PROPERTIES OF THE PERIOD 3

OXIDES
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These pages explain the relationship between the physical properties of the oxides
of Period elements (sodium to chlorine) and their structures! "rgon is obviously
omitted because it doesn#t form an oxide!
A quick summary of the trends
The oxides
The oxides we#ll be loo$ing at are%
Na
&
' (g' "l
&
'

)i'
&
P
*
'
+,
)'

-l
&
'
.
P
*
'
/
)'
&
-l
&
'
Those oxides in the top row are $nown as the highest oxides of the various
elements! These are the oxides where the Period elements are in their highest
oxidation states! 0n these oxides, all the outer electrons in the Period element
are being involved in the bonding - from 1ust the one with sodium, to all seven of
chlorine#s outer electrons!
The structures
The trend in structure is from the metallic oxides containing giant structures of
ions on the left of the period via a giant covalent oxide (silicon dioxide) in the
middle to molecular oxides on the right!
Melting and boiling points
The giant structures (the metal oxides and silicon dioxide) will have high melting
and boiling points because a lot of energy is needed to brea$ the strong bonds (ionic
or covalent) operating in three dimensions!
1
The oxides of phosphorus, sulphur and chlorine consist of individual molecules -
some small and simple2 others polymeric!
The attractive forces between these molecules will be van der 3aals dispersion and
dipole-dipole interactions! These vary in si4e depending on the si4e, shape and
polarity of the various molecules - but will always be much wea$er than the ionic or
covalent bonds you need to brea$ in a giant structure!
These oxides tend to be gases, li5uids or low melting point solids!
Electrical conductivity
None of these oxides has any free or mobile electrons! That means that none of
them will conduct electricity when they are solid!
The ionic oxides can, however, undergo electrolysis when they are molten! They can
conduct electricity because of the movement of the ions towards the electrodes
and the discharge of the ions when they get there!
The metallic oxides
The structures
)odium, magnesium and aluminum oxides consist of giant structures containing
metal ions and oxide ions!
Melting and boiling points
There are strong attractions between the ions in each of these oxides and these
attractions need a lot of heat energy to brea$! These oxides therefore have high
melting and boiling points.
Electrical conductivity
None of these conducts electricity in the solid state, but electrolysis is possible if
they are molten! They conduct electricity because of the movement and discharge
of the ions present! The only important example of this is in the electrolysis of
aluminum oxide in the manufacture of aluminum!
3hether you can electroly4e molten sodium oxide depends, of course, on whether it
actually melts instead of subliming or decomposing under ordinary circumstances! 0f
it sublimes, you won#t get any li5uid to electroly4e6
2
(agnesium and aluminum oxides have melting points far too high to be able to
electroly4e them in a simple lab!
3
Silicon dioxide (silicon(I! oxide!
The structure
The electronegativity of the elements increases as you go across the period, and by
the time you get to silicon, there isn#t enough electronegativity difference between
the silicon and the oxygen to form an ionic bond! )ilicon dioxide is a giant covalent
structure"
There are three different crystal forms of silicon dioxide! The easiest one to
remember and draw is based on the diamond structure!
Melting and boiling points
)ilicon dioxide has a high melting point - varying depending on what the particular
structure is (remember that the structure given is only one of three possible
structures), but they are all around +.,,7-! 8ery strong silicon-oxygen covalent
bonds have to be bro$en throughout the structure before melting occurs! )ilicon
dioxide boils at &&,7-!
9ecause you are tal$ing about a different form of bonding, it doesn#t ma$e sense to
try to compare these values directly with the metallic oxides! 3hat you can safely
say is that because the metallic oxides and silicon dioxide have giant structures,
the melting and boiling points are all high!
Electrical conductivity
)ilicon dioxide doesn#t have any mobile electrons or ions - so it doesn#t conduct
electricity either as a solid or a li5uid!
The molecular oxides
Phosphorus, sulphur and chlorine all form oxides which consist of molecules! )ome
of these molecules are fairly simple - others are polymeric! 3e are 1ust going to
loo$ at some of the simple ones!
(elting and boiling points of these oxides will be much lower than those of the
metal oxides or silicon dioxide! The intermolecular forces holding one molecule to
its neighbors will be van der 3aals dispersion forces or dipole-dipole interactions!
The strength of these will vary depending on the si4e of the molecules!
4
None of these oxides conducts electricity either as solids or as li5uids! None of
them contains ions or free electrons!
The phosphorus oxides
Phosphorus has two common oxides, phosphorus (000) oxide, P
*
'
/
, and phosphorus
(8) oxide, P
*
'
+,
!
#hosphorus (III! oxide (tetraphosphorus hexoxide!
Phosphorus (000) oxide is a white solid, melting at &*7- and boiling at +.7-!
The phosphorus is using only three of its outer electrons (the unpaired p
electrons) to form bonds with the oxygens!
#hosphorus (! oxide (tetraphosphorus decoxide!
Phosphorus (8) oxide is also a white solid, subliming (turning straight from solid to
vapour) at ,,7-! 0n this case, the phosphorus uses all five of its outer electrons in
the bonding!
)olid phosphorus(8) oxide exists in several different forms - some of them
polymeric! 3e are going to concentrate on a simple molecular form, and this is also
present in the vapour!
This is most easily drawn starting from P
*
'
/
! The other four oxygens are attached
to the four phosphorus atoms via double bonds!
5
The sulphur oxides
)ulphur has two common oxides, sulphur dioxide (sulphur (08) oxide), )'
&
, and
sulphur trioxide (sulphur (80) oxide), )'

!
Sulphur dioxide
)ulphur dioxide is a colourless gas at room temperature with an easily recogni4ed
cho$ing smell! 0t consists of simple )'
&
molecules!
The sulphur uses * of its outer electrons to form the double bonds with the
oxygen, leaving the other two as a lone pair on the sulphur! The bent shape of )'
&

is due to this lone pair!
Sulphur trioxide
Pure sulphur trioxide is a white solid with a low melting and boiling point! 0t reacts
very rapidly with water vapour in the air to form sulphuric acid! That means that if
you ma$e some in the lab, you tend to see it as a white sludge which fumes
dramatically in moist air (forming a fog of sulphuric acid droplets)!
:aseous sulphur trioxide consists of simple )'

molecules in which all six of the

sulphur#s outer electrons are involved in the bonding!
There are various forms of solid sulphur trioxide! The simplest one is a trimer,
)

'
;
, where three )'

molecules are 1oined up and arranged in a ring!

The fact that the simple molecules 1oin up in this way to ma$e bigger structures is
what ma$es the sulphur trioxide a solid rather than a gas!
6
The chlorine oxides
-hlorine forms several oxides! <ere we are 1ust loo$ing at two of them = chlorine
(0) oxide (dichlorine monoxide), -l
&
', and chlorine (800) oxide (dichlorine
heptoxide), -l
&
'
.
!
$hlorine (I! oxide (dichlorine monoxide!
-hlorine (0) oxide is a yellowish-red gas at room temperature! 0t consists of simple
small molecules!
There#s nothing in the least surprising about this molecule and it#s physical
properties are 1ust what you would expect for a molecule this si4e!
$hlorine (II! oxide (dichlorine heptoxide!
0n chlorine (800) oxide, the chlorine uses all of its seven outer electrons in bonds
with oxygen! This produces a much bigger molecule, and so you would expect its
melting point and boiling point to be higher than chlorine (0) oxide!
-hlorine (800) oxide is a colourless oily li5uid at room temperature!
The diagram has been drawn as a standard structural formula for simplicity! 0n
fact, the shape is tetrahedral around both chlorines, and 8-shaped around the
central oxygen!
7
PROPERTIES OF THE PERIOD 3 CHLORIDES
This page loo$s at the structures of the chlorides of the Period elements (sodium
to sulphur>), their physical properties and their reactions with water!
-hlorine and argon are omitted - chlorine because it is meaningless to tal$ about
?chlorine chloride?, and argon because it doesn#t form a chloride!
A quick summary of the trends
The chlorides
The chlorides we#ll be loo$ing at are%
Na-l (g-l
&
"l-l

)i-l
*
P-l
@
)
&
-l
&
P-l

"s you will see later, aluminum chloride exists in some circumstances as a dimer,
"l
&
-l
/
!
The structures
)odium chloride and magnesium chloride are ionic and consist of giant ionic lattices
at room temperature
"luminum chloride and phosphorus (8) chloride are tric$y6 They change their
structure from ionic to covalent when the solid turns to a li5uid or vapour! There is
much more about this later on this page!
The others are simple covalent molecules!
Melting and boiling points
)odium and magnesium chlorides are solids with high melting and boiling points
because of the large amount of heat (energy) which is needed to brea$ the strong
ionic attractions!
8
The rest are li5uids or low melting point solids! Aeaving aside the aluminum chloride
and phosphorus (8) chloride cases where the situation is 5uite complicated, the
attractions in the others will be much wea$er intermolecular forces such as van der
3aals dispersion forces! These vary depending on the si4e and shape of the
molecule, but will always be far wea$er than ionic bonds!
Electrical conductivity
)odium and magnesium chlorides are ionic and so will undergo electrolysis when they
are molten! Blectricity is carried by the movement of the ions and their discharge
at the electrodes!
0n the aluminum chloride and phosphorus (8) chloride cases, the solid doesn#t
conduct electricity because the ions aren#t free to move! 0n the li5uid (where it
exists - both of these sublime at ordinary pressures), they have converted into a
covalent form, and so don#t conduct either!
The rest of the chlorides don#t conduct electricity either solid or molten because
they don#t have any ions or any mobile electrons!
%eactions &ith &ater
"s an approximation, the simple ionic chlorides (sodium and magnesium chloride)
1ust dissolve in water!
The other chlorides all react with water in a variety of ways described below for
each individual chloride! The reaction with water is $nown as hydrolysis!
The Individual $hlorides
Sodium chloride' (a$l
)odium chloride is a simple ionic compound consisting of a giant array of sodium and
chloride ions!
" small representative bit of a sodium chloride lattice loo$s li$e this%
9
This is normally drawn in an exploded form as%
The strong attractions between the positive and negative ions need a lot of heat
energy to brea$, and so sodium chloride has high melting and boiling points!
0t doesn#t conduct electricity in the solid state because it hasn#t any mobile
electrons and the ions aren#t free to move! <owever, when it melts it undergoes
electrolysis!
)odium chloride simply dissolves in water to give a neutral solution!
Magnesium chloride, MgCl
2
(agnesium chloride is also ionic, but with a more complicated arrangement of the
ions to allow for having twice as many chloride ions as magnesium ions! "gain, lots of
heat energy is needed to overcome the attractions between the ions, and so the
melting and boiling points are again high!
)olid magnesium chloride is a non-conductor of electricity because the ions aren#t
free to move! <owever, it undergoes electrolysis when the ions become free on
melting!
(agnesium chloride dissolves in water to give a faintly acidic solution (p< C
approximately /)!
3hen magnesium ions are bro$en off the solid lattice and go into solution, there is
enough attraction between the &D ions and the water molecules to get co-ordinate
(dative covalent) bonds formed between the magnesium ions and lone pairs on
surrounding water molecules!
<exaa5uamagnesium ions are formed, E(g(<
&
')
/
F
&D
!
10
0ons of this sort are acidic - the degree of acidity depending on how much the
electrons in the water molecules are pulled towards the metal at the centre of the
ion! The hydrogens are made more positive than they would otherwise be, and more
easily pulled off by a base!
0n the magnesium case, the amount of distortion is 5uite small, and only a small
proportion of the hydrogen atoms are removed by a base - in this case, by water
molecules in the solution!
The presence of the hydronium ions in the solution causes it to be acidic! The fact
that there aren#t many of them formed (the position of e5uilibrium lies well to the
left), means that the solution is only wea$ly acidic!
Gou may also find the last e5uation in a simplified form%
<ydrogen ions in solution are hydronium ions! 0f you use this form, it is essential to
include the state symbols!
Aluminum chloride' Al$l
)
Blectronegativity increases as you go across the period and, by the time you get to
aluminum2 there isn#t enough electronegativity difference between aluminum and
chlorine for there to be a simple ionic bond!
"luminum chloride is complicated by the way its structure changes as temperature
increases!
"t room temperature, the aluminum in aluminum chloride is /-coordinated! That
means that each aluminum is surrounded by / chlorines! The structure is an ionic
lattice - although with a lot of covalent character!
"t ordinary atmospheric pressure, aluminum chloride sublimes (turns straight from
solid to vapour) at about +H,7-! 0f the pressure is raised to 1ust over &
atmospheres, it melts instead at a temperature of +;&7-!
9oth of these temperatures, of course, are completely wrong for an ionic compound
- they are much too low! They suggest comparatively wea$ attractions between
molecules - not strong attractions between ions!
11
The coordination of the aluminum changes at these temperatures! 0t becomes *-
coordinated - each aluminum now being surrounded by * chlorines rather than /!
3hat happens is that the original lattice has converted into "l
&
-l
/
molecules!
This conversion means, of course, that you have completely lost any ionic character
- which is why the aluminum chloride vapori4es or melts (depending on the
pressure)!
There is an e5uilibrium between these dimers and simple "l-l

molecules! "s the

temperature increases further, the position of e5uilibrium shifts more and more to
the right!
)ummary
"t room temperature, solid aluminum chloride has an ionic lattice with a lot
of covalent character!
"t temperatures around +H, - +;,7- (depending on the pressure), aluminum
chloride coverts to a molecular form, "l
&
-l
/
! This causes it to melt or
vapori4e because there are now only comparatively wea$ intermolecular
attractions!
"s the temperature increases a bit more, it increasingly brea$s up into
simple "l-l

molecules!
)olid aluminum chloride doesn#t conduct electricity at room temperature because
the ions aren#t free to move! (olten aluminum chloride (only possible at increased
pressures) doesn#t conduct electricity because there aren#t any ions any more!
12
The aluminum chloride reacts with the water rather than 1ust dissolving in it! 0n the
first instance, hexaa5uaaluminum ions are formed together with chloride ions!
Gou will see that this is very similar to the magnesium chloride e5uation given above
- the only real difference is the charge on the ion!
That extra charge pulls electrons from the water molecules 5uite strongly towards
the aluminum! That ma$es the hydrogens more positive and so easier to remove
from the ion! 0n other words, this ion is much more acidic than in the corresponding
magnesium case!
These e5uilibria (whichever you choose to write) lie further to the right, and so the
solution formed is more acidic - there are more hydroxonium ions in it!
or, more simply%
Silicon tetrachloride' Si$l
*
)ilicon tetrachloride is a simple no-messing-about covalent chloride! There isn#t
enough electronegativity difference between the silicon and the chlorine for the
two to form ionic bonds!
)ilicon tetrachloride is a colourless li5uid at room temperature which fumes in
moist air! The only attractions between the molecules are van der 3aals dispersion
forces!
0t doesn#t conduct electricity because of the lac$ of ions or mobile electrons!
0t fumes in moist air because it reacts with water in the air to produce hydrogen
chloride! 0f you add water to silicon tetrachloride, there is a violent reaction to
produce silicon dioxide and fumes of hydrogen chloride! 0n a large excess of water,
the hydrogen chloride will, of course, dissolve to give a strongly acidic solution
containing hydrochloric acid!
13
The phosphorus chlorides
There are two phosphorus chlorides = phosphorus (000) chloride, P-l

, and
phosphorus (8) chloride, P-l
@
!
#hosphorus (III! chloride (phosphorus trichloride!' #$l
)
This is another simple covalent chloride - again a fuming li5uid at room temperature!
0t is a li5uid because there are only van der 3aals dispersion forces and dipole-
dipole attractions between the molecules!
0t doesn#t conduct electricity because of the lac$ of ions or mobile electrons!
Phosphorus (000) chloride reacts violently with water! Gou get phosphorous acid,
<

P'

, and fumes of hydrogen chloride (or a solution containing hydrochloric acid if

lots of water is used)!
#hosphorus (! chloride (phosphorus pentachloride!' #$l
+
Infortunately, phosphorus (8) chloride is structurally more complicated!
Phosphorus (8) chloride is a white solid which sublimes at +/7-! The higher the
temperature goes above that, the more the phosphorus (8) chloride dissociates
(splits up reversibly) to give phosphorus (000) chloride and chlorine!
)olid phosphorus (8) chloride contains ions - which is why it is a solid at room
temperature! The formation of the ions involves two molecules of P-l
@
!
" chloride ion transfers from one of the original molecules to the other, leaving a
positive ion, EP-l
*
F
D
, and a negative ion, EP-l
/
F
-
!
"t +/7-, the phosphorus (8) chloride converts to a simple molecular form
containing P-l
@
molecules! 9ecause there are only van der 3aals dispersion forces
between these, it then vapori4es!
)olid phosphorus (8) chloride doesn#t conduct electricity because the ions aren#t
free to move!
14
Phosphorus (8) chloride has a violent reaction with water producing fumes of
hydrogen chloride! "s with the other covalent chlorides, if there is enough water
present, these will dissolve to give a solution containing hydrochloric acid!
The overall e5uation in boiling water is%
,-isulphur dichloride' S
.
$l
.
,
Jisulphur dichloride is a simple covalent li5uid - orange and smelly6
The shape is surprisingly difficult to draw convincingly6 The atoms are all 1oined up
in a line - but twisted%
The reason for drawing the shape is to give a hint about what sort of
intermolecular attractions are possible! There is no plane of symmetry in the
molecule and that means that it will have an overall permanent dipole!
The li5uid will have van der 3aals dispersion forces and dipole-dipole attractions!
There are no ions in disulphur dichloride and no mobile electrons - so it never
conducts electricity!
Jisulphur dichloride reacts slowly with water to produce a complex mixture of
things including hydrochloric acid, sulphur, hydrogen sulphide and various sulphur-
containing acids and anions (negative ions)! There is no way that you can write a
single e5uation for this - and one would never be expected in an exam!
15
Summary
+! #hysical properties of oxides/ The physical properties of these oxides
depend on the type of bonding!
Na
&
', "l
&
'

and (g' are ionic oxides and hence have a high melting point! (g' and
"l
&
'

have a higher melting point than Na

&
' since the charges are higher, resulting
in a stronger attraction between the ions!
)i'
&
has a giant covalent structure and hence a high melting point! There are strong
covalent bonds between all the atoms and thus lots of energy is re5uired to brea$
them!
P
*
'
+,
and )'

are molecular covalent and so only intermolecular forces exist

between the molecules! The melting points are thus much lower! P
*
'
+,
is a much
bigger molecule than )'

and so has a much higher melting point, as the van der

3aals forces are stronger!
Blement Na (g "l )i P )
Kormulae of
oxide
Na
&
' (g' "l
&
'

)i'
&
P
*
'
+,
)'

)tructure of
oxide
0onic 0onic (ostly
ionic
:iant
covalent
(olecular
covalent
(olecular
covalent
(elting point of
oxide L7-
+&.@ &H@& &,.& +., ,, -+,
&! Acid0base character of oxides
0onic oxides contain the '
&-
ion! This is a strongly basic ion which reacts with water
to produce hydroxide ions%
'
&-
(a5) D <
&
'(l) &'<
-
(a5)
Thus all ionic oxides are 9")0-!
-ovalent oxides do not contain ions, but have a strongly positive dipole on the atom
which is not oxygen! This attracts the lone pair on water molecules, releasing <
D

ions%
16
('(s) D <
&
'(l) ('('<)
-
(a5)D <
D
(a5)
Thus all covalent oxides are "-0J0-!
0ntermediate oxides can react in either of the above ways, depending on the
conditions! They can thus behave as either acids or bases and are thus
"(P<'TBM0-!
(a
.
1 is a basic oxide! 0t dissolves in water to give an al$aline solution (p< C +*)! 0t
also reacts with acids%
Na
&
'(s) D <
&
'(l) &Na'<(a5)
Na
&
'(s) D &<
D
(a5) &Na
D
(a5) D <
&
'(l)
Mg1 is a basic oxide! 0t is only slightly soluble in water and so the solution is only
slightly al$aline (p< C ;)! 0t reacts readily with acids%
(g'(s) D <
&
'(l) (g('<)
&
(s) (g('<)
&
(a5)
(g'(s) D &<
D
(a5) (g
&D
(a5) D <
&
'(l)
Al
.
1
)
is an amphoteric oxide! 0t is insoluble in water (p< C .) but dissolves in both
acids and al$alis%
"l
&
'

(s) D /<
D
(a5) &"l
D
(a5) D <
&
'(l)
"l
&
'

(s) D <
&
'(l) D /'<
-
(a5) &"l('<)
/
-
(a5)
"l
&
'

(s) D <
&
'(l) D &'<
-
(a5) &"l('<)
*
-
(a5)
Si1
.
is an acidic oxide! 0t is insoluble in water (p< C .) but dissolves in hot
concentrated al$alis%
)i'
&
(s) D &'<
-
(a5) )i'

&-
(a5) D <
&
'(l)
#
*
1
23
is an acidic oxide! 0t dissolves in water to give acidic solutions and is also
soluble in al$alis%
P
*
'
+,
(s) D /<
&
'(l) *<

P'
*
(a5) p< C
S1
.
and S1
)
are acidic oxides! They dissolve in water to give acidic solutions, and
also react with al$alis%
17
)'
&
(g) D <
&
'(l) CC <
&
)'

(a5), p< C &

)'

(g) D <
&
'(l) <
&
)'
*
(a5), p< C +
)'
&
is a waste gas in many industrial processes! 0t is harmful because it dissolves in
rain water to give acid rain! 0t can be removed from waste gases because it
dissolves in al$ali and so it is passed through an al$aline solution in waste gas outlets
to minimi4e the amount which escapes into the atmosphere!
T4E $451%I-ES 16 #E%I1- ) E5EME(TS
"ll the elements of Period except argon combine directly with chlorine to give
chlorides!
&Na(s) D -l
&
(g) &Na-l(s)
(a$l is an ionic chloride!
(g(s) D -l
&
(g) (g-l
&
(s)
Mg1 is also an ionic chloride!
&"l(s) D -l
&
(g) &"l-l

(s)
Al$l
)
is covalent! 0t forms a polymeric structure in the solid state, turning 5uic$ly
on heating into a dimeric gas ("l
&
-l
/
)! 0t thus behaves as a simple molecular chloride!
)i(s) D &-l
&
(g) )i-l
*
(s)
Si$l
*
is a molecular covalent chloride!
P
*
(s) D /-l
&
(g) *P-l

(s)
P-l
@
is formed by reacting P-l

with excess chlorine in a reversible reaction%

P-l

(l) D -l
&
(g) CC P-l
@
(s)
#$l
+
is actually ionic in the solid state - it exists as EP-l
*
F
D
EP-l
/
F
-
in the solid state!
18
The acid-base properties of the oxides of Period can be summari4ed in the
following table%
Blement Na (g "l )i P )
Kormulae of
oxides
Na
&
' (g' "l
&
'

)i'
&
P
*
'
+,
)'
&
)'

"cid-base
character of
oxide
9asic 9asic "mphoteric "cidic "cidic "cidic
p< of solution
when dissolved
in water
+& - +* H - ;
.
insoluble
.
insoluble
& - *
& - *
()'
&
)
+ -
()'

)
The oxides therefore become more acidic on moving from left to right in the
periodic table!
#hysical properties of chlorides
(a$l and Mg$l
.
are ionic chlorides! )ince a large amount of energy is re5uired to
separate the ions, the melting point is high!
Al$l
)
and Si$l
*
are molecular covalent chlorides, and so only intermolecular forces
exist between the molecules! The melting points are thus much lower than the ionic
chlorides!
"l-l

actually exists in polymeric form in the solid state, which is converted to a

dimeric form in the gas phase! "t high temperatures, it reverts to a simple
molecular structure%
Al
Cl
Cl
Cl
Al
Cl
Cl
Cl
n

Al
Al
Cl Cl
Cl
Cl
Cl
Cl
n/2
n
complex polymer dimer
monomer
(solid)
(gas - at low T)
(gas - at high T)
19
The aluminum atom is electron deficient = it has only of its four valence orbitals
occupied, so it has an empty orbital with which it can accept a lone pair of electrons
from a -l atom on an ad1acent monomer!
#$l
+
is ionic so its melting point is thus high! 'n heating, however, it reverts to a
simple covalent structure and sublimes!
Blement Na (g "l )i P
Kormula of
chloride
Na-l (g-l
&
"l-l

)i-l
*
P-l
@
)tructure of
chloride
ionic ionic polymer molecular
covalent
0onic
(elting point of
chloride L7-
H,+ .+, +H* @H +/&
%eaction of chlorides &ith &ater
The way in which chlorides react with water depends on the type of bonding
present in the chloride%
Ionic chlorides dissolve in water to give neutral solutions%
Na-l(s) Na
D
(a5) D -l
-
(a5) p< C .
(g-l
&
(s) (g
&D
(a5) D &-l
-
(a5) p< C .
Aluminium chloride reacts with water to give hydrated aluminum ions and chloride
ions! The hydrated aluminium ions undergo deprotonation to give an acidic solution%
"l-l

(s) D /<
&
'(l) "l(<
&
')
/
D
(a5) D -l
-
(a5)
"l(<
&
')
/
D
(a5) D <
&
'(l) E"l(<
&
')
@
('<)F
&D
(a5) D <

'
D
(a5)
The other covalent chlorides react readily with water at room temperature to
form the oxide or hydroxide and <-l(g)! The <-l is formed as white misty fumes,
and the observance of these fumes is a good indication that the chloride is
covalent!
)i-l
*
(l) D &<
&
'(l) )i'
&
(s) D *<-l(g) p< C + - &
P-l
@
(s) D *<
&
'(l) <

P'
*
(a5) D @<-l(g) p< C + - &
$ovalent chlorides thus react with water to give acidic solutions! The acidity is due
to dissolved <-l.
20
The water molecules attac$ the covalent chlorides by donating lone pairs of
electrons into empty low-lying orbitals on the electropositive atoms! 0n the case of
"l-l

, there is an available p orbital, and in )i-l

*
and P-l
@
there are available d-
orbitals%
s p
d
"l-l

ENeF

)i-l
*
ENeF

P-l
@
ENeF

0t the availability of these low-lying empty orbitals which enables these chlorides
to react readily with water!
%eaction of $l
.
&ith &ater
-l
&
(g) D <
&
'(l) <-l'(a5) D <-l(a5)
The resulting solution contains <-l(a5) and is thus acidic (p< C &)!
21