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Trends in Period 3

M+ X- ionic bond, M+-X+ polar bond and M-X a relatively non-polar bond (no
partial charges shown)
Element

Sodi Magnesi Aluminiu Silico Phosph


Sulfur Chlorine
um
um
m
n
orus

old/latest G
roup
Symbol

1
11

Na

2
12

Mg

3/13
Al

13

4/14
Si

14

5/15
15

solid
met
solid
solid
solid
solid
allic
metallic metallic giant small
Structure latti
lattice
lattice covale covale
of
ce of
of
of
nt
nt
element Na+a
Mg2+ an Al3+and lattice molecu
nd
d free e- free eSin
les P4
free
e
electron
[Ne]3
configurat
[Ne]3s2
s1
ion

common
+1
+2
oxidation
states e.g.
max
in oxides,
max +2
+1
chlorides,
hydrides

electrone
gativity of 0.93
element
Na2O
formula of
,
oxides Na2O

1.31

16

7/17
17

Cl

0/18
Ar

18

solid
small gaseous
gaseou
covale
small
s
nt
covalent
single
molec molecule
atoms
ules
s Cl2
S8

[Ne]3s23 [Ne]3s [Ne]3s2 [Ne]3s [Ne]3s23p [Ne]3s2


2
2
5
p1
3p2
3p3
3p4
3p6

+3

+4

-2, -2,
+3, +5 +4,
+6
max
+5
max
+6

at Xe
can get
max of
+8
compou
max +7 nds but
not
here!
-1, +1,
+3, +5,
+7

max +3

max
+4

1.61

1.90

2.19

2.58

3.16

3.20

SiO2

P4O6,
P4O10

SO2,
SO3

Cl2O, ClO2
,Cl2O6,
Cl2O7

MgO

Al2O3

ionic
lattice

ionic
lattice

bonding ionic
and
latti
structure ce
of oxides

6/16

Argon

solid
solid covale covalent
covale covale
nt
small
nt
nt
small gas/liquid
giant small gaseo molecule
struct molecu
us
s

ure
electrone
gativity
difference
X-O (O is
3.44)
nature of
bond

2.51
2.13
+

Na
O2-or Mg2+ O2O22-

formula of
NaCl
chlorides

bonding ionic
in
latti
chlorides ce

Formula
NaH
of hydride

1.54

molec
ules

1.25

0.86

0.28

Al3+ O2-

Si+O-

MgCl2

AlCl3

SiCl4

PCl3,
PCl5

S2Cl2,
??

Cl2

ionic
lattice

ionic
lattice,
vaporise
s to
covalent
dimer
molecul
es Al2Cl6

covale
nt
small
liquid
molec
ules

liquid
covale
nt
small
molecu
les

covale
nt
small
liquid
molec
ules

covalent
small
diatomic
gaseous
molecule

electrone
gativity 2.23
1.85
difference
X-Cl (Cl is Na+
Mg2+ Cl3.16)
Hnature of
bond
MgH2

'polymer
-like'
structur
bonding
ionic
e of
and
latti interme
structure
ce
diate
of hydride
ionic/cov
alent
nature
electrone
gativity 1.27
0.89
difference
X-H (H is Na+
Mg+-H2.20)
Hnature of
bond

1.83

les

1.55

1.26

P+-O- S+-O-

1.25

Cl-O

0.58

0.00

Al3+ Cl-

Si+Cl-

P+-Cl-

S+Cl-

Cl-Cl

AlH3

SiH4

PH3

H2S

HCl

'polymer
-like'
structur
e of
interme
diate
ionic/cov
alent
nature

small
covale
nt
gaseo
us
molec
ule

small
covale
nt
gaseou
s
molecu
le

0.59

0.30

0.01

0.38

0.96

Al+-H-

Si-H

P-H

H+-S-

H+-Cl-

small
covale
small
nt
covalent
gaseo
gaseous
us
molecule
molec
ule

The structure and physical properties of the elements

The trend is metal lattice ==> giant covalent structure ==>


small covalent molecules

Sodium Na, magnesium Mg and aluminium Al are silvery solids, with a


metal lattice structure, high boiling points and are good conductors of
heat/electricity due to the delocalised free electrons moving between
the immobile metal ions.

Si has a non-metallic giant covalent structure based on a tetrahedral


arrangement of S-Si bonds and is a poor conductor of heat/electricity.

The strong 3D bonding gives silicon a high melting/boiling point


and great hardness.

Phosphorus P4, sulfur S8 and chlorine Cl2 are simple-small covalent


molecules and Ar consists of single atoms. The molecules are only held
together by the weakest of the intermolecular forces, namely the
instantaneous dipole - induced dipole forces, and consequently have
very low melting/boiling points.

The melting/boiling points increase from Na ==> Mg ==> Al


due to 1 ==> 2 ==> 3 potential number of delocalised
electrons that may contribute to bonding.

From left to right the elements become less metallic and


more non-metallic.

Electron configuration and oxidation states


o

Electron configurations of 2,8,1 or 1s22s22p63s1 to 2,8,8


or 1s22s22p63s23p6

Filling the s orbital (max 2 e-'s) gives the metallic s-block


elements of Groups 1-2,

filling the p orbitals gives the predominantly non-metallic p block


elements of Group 3-7, 0 (Gps 13-18) bar aluminium for Period
3.

Oxidation states in compounds (numerically = valency) are: sodium


Na (+1 only), magnesium Mg (+2 only), aluminium Al (+3 only), Si (+4,
-4 with electropositive metals), P (usually -3, +3 or +5), S (-2, +4 and
+4), Cl (-1, +1, +3, +5 and +7), Ar has no stable compounds due to
the full outer quantum level (shell) being full, conferring extra
electronic stability on the atom.

From Na to Cl the maximum oxidation state is equal to the 'old'


group number and the 'highest' oxide formulae can be predicted
up to chlorine and the chloride formula up to P (there is no
stable SCl6 but there is a ClF7.

So in the 'highest' oxides you can go from +1 to +7 for


groups 1 to 7/17

(at Xe on Period 5 you can reach +8, but not for Ar)

Na2O, MgO, Al2O3, SiO2, P4O10 (= P2O5), SO3, Cl2O7 (at Xe


you can have XeO4)

i.e. using all available 1-7 outer 3s and 3p electrons


(valence electrons) are all used in the bonding of the
highest possible oxide.

and similarly in the 'highest' chlorides (upto Group 5), and


fluorides (for Groups 6 and 7) you also go from maximum
oxidation state of +1 to +7 in the halide compounds
irrespective of bond character.

NaCl, MgCl2, AlCl3, SiCl4, PCl5, SF6, ClF7 (at Xe you can have
XeF8)

Reaction of element with oxygen and the structure of the oxide

(Gp 1) 4Na(s) + O2(g) ==> 2Na2O(s) and


Na2O2 on heating the metal in air

(Gp 2) 2Mg(s) + O2(g) ==> 2MgO(s) on


heating metal in air

(Gp 3) 4Al(s) +
3O2(g) ==> 2Al2O3(s) needs high
temperature

(Gp 4) Si(s) + O2(g) ==> SiO2(g) needs


high temperature

(Gp 5) P4(s) + 5O2(g) ==> P4O10(s) on


heating in air

(Gp 6) S(s) + O2(g) ==> SO2(g) and a little


SO3 on heating in air

(Gp 7) Chlorine - no reaction

(Gp 0) Argon - no reaction

Reaction with oxygen and oxide structure


o

The metals Na, Mg and Al burn to form a giant ionic oxide lattices

sodium oxide/peroxide, magnesium oxide and aluminium


oxide ...

(Na+)2O2- and (Na+)2O22-, Mg2+O2- and (Al3+)2(O2-)3 respectively.

Silicon Si forms a giant covalent lattice of (SiO 2)n where n is very larger
number

Phosphorus P forms two simple molecular covalent solid oxides


P4O6 and P4O10.

Sulphur/sulfur S can form two simple molecular covalent gas molecules


SO2 and SO3

Chlorine Cl forms oxide molecules of Cl2O, Cl2O7 (and others).

Argon has no reaction.

The overall pattern, from left to right is

giant ionic lattice => giant covalent lattice ==> small


covalent molecules.

The change in bonding character from ionic to covalent in the oxide,


follows the decreasing difference in electronegativity between that of
the period 3 element and oxygen.

Reaction of the oxides with water, acids and alkalis

(Gp 1) Na2O(s) +
H2O(l) ==> 2NaOH(aq) pH 13-14
strong base
or Na2O2(s) + 2H2O(l) ==> 2NaOH(aq) +
H2O2(aq)

(Gp 2) MgO(s) +
H2O(l) ==> Mg(OH)2(aq/s) ~pH 11-12
weak base

(Gp 3) Al2O3, insoluble, no reaction with


water, but amphoteric with respect to
acids and strong alkalis

(Gp 4) SiO2, insoluble, no reaction with


water, but weakly acidic and will dissolve
a little in strong alkali e.g. conc.
NaOH(aq)

(Gp 5) P4O6(s) + 6H2O(l) ==>


4H3PO3(aq) ~pH 2 weak acid

(Gp 6) SO2(aq) + H2O(l) <=> H+(aq) +


HSO3-(aq) pH 2-3 weak acid

P4O10(s) + 6H2O(l) ==> 4H3PO4(aq) pH 1 SO3(g) + H2O(l) ==> H2SO4(aq) pH 0-1


strong acid
strong acid
(Gp 7) Cl2O(g) +
H2O(l) ==> 2HClO(aq) ~pH 3? weak
acid

(Gp 0) argon has no oxide

Cl2O7(l) + H2O(l) ==> 2HClO4(aq) pH 1


strong acid

The chemical character of the oxides - reaction of the Period 3


oxides with water, acids or alkalis.
o

Sodium oxide/peroxide Na2O/Na2O2 and magnesium oxide MgO


are basic and form an alkali in water and salts with acids.

MgO(s) + 2HCl(aq) ==> MgCl2(aq) + H2O(l)

Aluminium oxide Al2O3 has no reaction, insoluble, but


is amphoteric and forms salts with acids and alkalis.

Al2O3(s) + 6HCl(aq) ==> 2AlCl3(aq) + 3H2O(l)

Al2O3(s) + 2NaOH(aq) + 3H2O(l) ==> 2Na[Al(OH)4](aq)

Silicon(IV) oxide (silicon dioxide) SiO2 has no reaction but is weakly


acidic forming salts with alkalis.

Phosphorus(III) oxide P4O6 and phosphorus(V) oxide P4O10 are


moderately-strong acidic oxides forming phosphoric(III) acid H 3PO3 and
phosphoric(V) acid H3PO4 on reaction with water.

Generally speaking, in a series of oxides for the same element,


the higher the oxidation state of X in a 'XxOy' series, the more
acidic is the oxide, so H3PO4 is a stronger acid than H3PO3.

The oxides or acids are readily neutralised to give phosphate


salts e.g.

H3PO4 (aq) + NaOH(aq) ==> NaH2PO4(aq) + H2O(l)

Two further reactions are possible with the sodium hydroxide to


give Na2HPO4 and Na3PO4.

Chlorine(I) oxide Cl2O and chlorine(VII) oxide Cl2O7 are moderate to


strong acidic in water.

The overall patterns, from left to right across Period 3 is ...

giant ionic lattice ==> small covalent molecules

In terms of overall chemical character ...

The change in bonding character from ionic to covalent in the


oxide follows the decreasing difference in electronegativity
between that of the element and oxygen.

metal basic oxides ==> amphoteric oxides ==> nonmetal oxides

This is chemically characteristic of metallic ==> non-metallic


element character.

Reaction of element with chlorine and the structure of the chloride

(Gp 1) 2Na(s) + Cl2(g) ==> 2NaCl(s)

(Gp 2) Mg(s) + Cl2(g) ==> MgCl2(s)

(Gp 3) 2Al(s) + 3Cl2(g) ==> 2AlCl3(s)

(Gp 4) Si(s) + 2Cl2(g) ==> SiCl4(l)

(Gp 5) P4(s) + 3Cl2(g) ==> 4PCl3(l)


P4(s) + 5Cl2(g) ==> 4PCl5(s)

(Gp 6) 2S(s) + Cl2(g) ==> S2Cl2(l) also


unstable SiCl2, SiCl4

(Gp 7) chlorine itself

(Gp 0) no reaction with argon

Reaction with chlorine and chloride structure


o

All of Na to S will combine directly on heating in chlorine to


give the chloride.

Sodium, magnesium and aluminium give giant ionic lattices

sodium chloride Na+Cl-, magnesium chloride Mg2+(Cl-)2 and


aluminium chloride Al3+(Cl-)3 respectively.

Note that aluminium chloride on heating sublimes above 180 oC


to form small Al2Cl6 covalent dimer molecules.

The non-metal elements give covalent chlorides.

Silicon forms the molecular covalent liquid silicon(IV) chloride


SiCl4 (silicon tetrachloride)

Phosphorus forms phosphorus(III) chloride PCl3 (phosphorus


trichloride) with limited chlorine

and phosphorus(V) chloride PCl5 (phosphorus pentachloride)


with excess chlorine.

Sulphur gives disulfur dichloride S2Cl2. by direct combination (and


unstable SCl2 and SCl4 can also be formed).

There is no stable argon chloride.

The overall pattern, from left to right across period 3 is ...

giant ionic lattice => polymeric covalent lattice ==> small


covalent molecules.

This is chemically characteristic of metallic ==> nonmetallic element character.

The change in bonding character from ionic to covalent in the


chloride, follows the decreasing difference in electronegativity
between that of the element and oxygen, as in the case of
oxides.

The formulae largely follow a pattern of rising formulae based on


the use of all outer electrons in bonding (1-5) and then a decline
in valency (oxidation state of the Period 3 element).

NaCl (+1), MgCl2 (+2), AlCl3 (+3), SiCl4 (+4), PCl5 (+5), S2Cl2 (
+1), Cl2, Ar no chloride

So the number of atoms of chlorine combined with the Period 3


element (the valency) follows the pattern

1 2 3 4 5 1 1 0

Reaction of the chlorides with water

(Gp 1) NaCl(s) + aq ==> Na+(aq) + Cl(aq) just dissolves, ~pH 7

(Gp 2) MgCl2(s) + aq ==> Mg2+(aq) + 2Cl(aq) just dissolves, ~pH 7

(Gp 3) AlCl3(s) +
(Gp 4) SiCl4(l) + 2H2O(l) ==> SiO2(s) +
3H2O(l) ==> Al(OH)3(s) + 3HCl(g) with 4HCl(aq) hydrolysis to give strongly
limited water you get hydrolysis to acid solution
give acid fumes
AlCl3(s) + aq ==> Al3+(aq) + 3Cl(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
give weakly acid solution

(Gp 6) S2Cl2(g) + H2O(l) ==> HCl(aq), S(s),


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 strongly
solution is quite acidic
acid solution
(Gp 7) chlorine itself

Gp 0 argon has no chloride

Reaction of the chloride with water


o

The ionic sodium chloride NaCl and magnesium chloride MgCl 2 dissolve
in water to form a nearly neutral solution of hydrated ions.

The ionic AlCl3 and the covalent all hydrolyse to form acid
solutions.

aluminium chloride Al2Cl6 ==> hydrochloric acid or weakly acidic


aluminium ion

silicon(IV) chloride SiCl4, (silicon tetrachloride) ==> hydrated


silicon dioxide + hydrochloric acid

phosphorus(III) chloride PCl3 (phosphorus trichloride) ==>


phosphoric(III) acid + hydrochloric acid

with phosphorus(V) PCl5 (phosphorus pentachloride) ==>


phosphoric(V) acid + hydrochloric acid

Phosphorus(III) chloride hydrolyses rapidly and


exothermically to form phosphoric(III) acid.

PCl3(l) + 3H2O(l) ==> H3PO3(aq) + 3HCl(aq)

Phosphorus(V) chloride initially hydrolyses to form


phosphorus oxychloride and hydrochloric acid.

(i) PCl5(s) + H2O(l) ==> POCl3(aq) + 2HCl(aq)

If the aqueous solution is boiled, phosphoric(V) acid


is formed and more hydrochloric acid.

(ii) POCl3(aq) + 3H2O(l) ==> H3PO4(aq) + 3HCl(aq)

overall (i) + (ii): PCl5(s) + 4H2O(l) ==> H3PO4(aq) +


5HCl(aq)

and disulphur dichloride S2Cl2 ==> a variety products including


acidic sulphur dioxide and hydrochloric acid.

The general trend is for ionic metal chloride salts to give nearly
neutral solutions => metal/non-metal covalent chlorides that
hydrolyse to give acidic solutions.

Reaction of element with water

(Gp 1) 2Na(s) + 2H2O(l) ==> 2NaOH(aq) + (Gp 2) Mg(s) + 2H2O(l) ==>


H2(g)
Mg(OH)2(aq) + H2(g)
(Gp 3) aluminium has no reaction with
water

(Gp 4) silicon has no reaction with water

(Gp 5) phosphorus has no reaction with


water

(Gp 6) sulfur has no reaction with water

(Gp 7) Cl2(g) + H2O(l) <=> HClO(aq) +


HCl(aq)

(Gp 0) argon has no reaction with water

Reaction of element with water


o

The reactive metal sodium Na rapidly gives the alkaline sodium


hydroxide and hydrogen,

as does magnesium Mg BUT much more slowly.

Aluminium Al, silicon Si, phosphorus P and sulfur S have no reaction


with water.

Chlorine, Cl2 forms a weakly acidic solution in water.

Argon has no reaction.

The 'limited' pattern for period 3 (or any other period), is to


have reactive metals on the left forming an alkaline solution
and a reactive non-metal on the right forming an acid solutions
IF they react with water.

The hydrides MHx


o

For hydrides the difference in electronegativity works both ways!

From left to right across the period you change from an

ionic sodium hydride crystal lattice Na+H-

to small non-polar molecule covalent hydrides (silane SiH 4 and


phosphine PH3)

and then a weakly acidic polar covalent hydride molecule


(hydrogen sulfide H2S)

and finally a strongly acidic polar covalent molecule (hydrogen


chloride HCl).

The formulae follow a simple period pattern of rising and falling


valency for the Period 3 elements.

NaH MgH2 AlH3 SiH4 PH3 H2S HCl (Ar)

the element valency pattern being 1 2 3 4 3 2 1 0

On reaction with water, the ionic metal hydrides at the start of the
period give an alkaline solution

e.g. NaH(s) + H2O(l) ==> NaOH(aq) + H2(g)

In the middle are neutral hydrides like phosphine which in contact with
water do not change the pH.

Then you get weakly acidic ==> strongly acidic hydrides when they
dissolve in water e.g.

weak acid: H2S(aq) + H2O(l) <=> H3O+(aq) + HS-(aq)

strong acid: HCl(aq) + H2O(l) ==> H3O+(aq) + Cl-(aq)

So things are a bit complicated with hydrides on period 3 due to the


left and right sided differences in electronegativity!

You go from X+H- ==> X+-H ==> X-H ==> X-H+

Radii of isoelectronic ions

Isoelectronic means species having the same total number of


electrons.

The table below considers the isoelectronic cations and anions associated
with Periods 2, 3 and 4.

isoele
ctroni
c
syste
m
Perio
d

(G
Gr
Gr Gr
Gro
ro
Gro
ou
ou ou
Gro
up
up
Gro up
p
p p
up
5/1
0/
up 2 3/1
4/
6/ 7/
1
5
18
3
14
16 17
)
Period 2

Period 3

[Ne]
10e
O2
(N
Mg2
C4- N3- - FNa+ + Al3+
2
1s 2s
e)
2
2p6
total
nucle
(+
+
+1
ar +6 +7
+9 10
+12 +13
8
1
charg
)
e
radiu
(3
s in
8pico 26
14 13
171
11 95
metr 0
0 6
2*
e
)
(pm)

65

50

ca
ox flu (n
mag alu
name
nitr
sod
rbi
id ori eo
nesi min
of ion
ide
ium
de
e de n)
um ium
Perio
d

Period 3

Period 4

[Ar]
18e
Si4
(Ar
1s22s - P3- S2- ClK+ Ca2+ Sc3+
)
2
6
2p 3
s23p6
nucle
(+
ar +1
+ +1
+1
+15
18
+20 +21
charg 4
16 7
9
)
e
radiu 27 212 18 18 (7 133 99
s in 1
4 1 1pico
15
metr
4*

81

e
(pm)

sil pho su chl (ar pot


sca
name
calc
ici sph lfi ori go assi
ndi
of ion
ium
de ide de de n) um
um

Excluding the noble gases themselves where this is frankly, something of a


data problem!,
o

there is a clear pattern of decreasing ionic radius with increase


in total nuclear charge (+ atomic/proton number) for the two
isoelectronic series tabulated above,

based on the electron configurations of neon and argon.