Chemistry of the Elements

PERIOD THREE SODIUM TO ARGON

Na

Mg

Al

FIGURE 1.1 Elements Of Period Three

ELECTRONIC CONFIGURATION
Eight (8) elements are found in Period Three namely:
Sodium
Magnesium
Aluminum
Silicon
Phosphorus
Sulphur
Chlorine
Argon

[Na]
[Mg]
[Al]
[Si]
[P]
[S]
[Cl]
[Ar]

1s2
1s2
1s2
1s2
1s2
1s2
1s2
1s2

2s2
2s2
2s2
2s2
2s2
2s2
2s2
2s2

2p6
2p6
2p6
2p6
2p6
2p6
2p6
2p6

3s1
3s2
3s2
3s2
3s1
3s1
3s1
3s1

3p1
3p2
3p3
3p4
3p5
3p6

Si

Cl

Ar

Chemistry of the Elements

1.1

PHYSICAL PROPERTIES
There is a gradual increase in electronegativity (electron attracting power) from left to right of
the periodic table.
Na

Mg

Al

Si

Cl

0.9

1.2

1.5

1.8

2.1

2.5

3.0

Increasing Electronegativity
TABLE 1.1 The Electronegativities Of Period Three

Atomic

Na

Mg

Al

Si

Cl

0.156

0.136

0.125

0.117

0.110

0.104

0.099

0.095

0.085

0.050

0.212

0.184

0.181

11+

12+

13+

14+

15+

16+

17+

Na+

Mg2+

Al3+

P3-

S2-

Cl-

Radius (nm)
Ionic Radius
(nm)
TABLE 1.2
Charge And
Ions Of
Three

Nuclear
Charge
Ion

The Size,
Common
Period

The changing properties across a period are related to the change in:
Nuclear Charge
Size Of The Atom
Increasing Number Of Outer Shell Electrons
The major properties which change across a period are:

Structure And Bonding

Acid/Base Properties
Redox Properties
Solubility And Complexing Properties

CHANGES OF PROPERTIES ACROSS PERIOD THREE

The number of protons within the nucleus increases, so do the electrons. A complete shell is
reached at the noble gas argon, so that screening is not felt. What is felt is the increasing nuclear
charge that holds the electrons more tightly. This is why the ionization energy of the elements
increases across a period.

Chemistry of the Elements

As a result the elements become more difficult to ionize and tend to attract electrons towards
them. This reduces the metallic character from left to right and with this change goes the mature
of the hydrides, oxides and chlorides.

Mg

Na

Al

Si

Cl

Ar

(White)

Melting Point

98

650

660

1410

44

119

-101

-189

890

1120

2450

2680

280

445

-34

-186

0.97

1.74

2.70

2.33

1.82

2.07

1.57

1.40

10

16

38

10-16

10-22

1.34

1.6

2.1

0.84

2.9 *

8*

1.7 * 10-5

10-4

10-5

( C)
o

Boiling Point
(oC)
Density (g cm3

TABLE 1.3
Properties
Elements In

Atomic
Conductance
(ohm-1 cm-4)
Thermal
Conductivity
(J cm-1 s-1 K-1)

STRUCTURE
GIANT

GIANT METALLIC
Na

Mg

SIMPLE MOLECULAR

MOLECULAR

Al

Si

Cl

TYPE OF ELEMENT
METALS
Na

Mg

Al

METALLOID
Si

TABLE 1.4 Grouping According To Metallic Character

TABLE 1.5 Grouping According To Structure

NON METALS
P

Cl

Ar

Ar

Physical
Of The
Period Three

Chemistry of the Elements

With reference to tables 3, 4 and 5, it should be observed that the physical properties of period
three (3) elements vary with increasing values from sodium to aluminum or silicon and drops
suddenly from phosphorous to argon.
The physical properties of the elements as mentioned in the table above are related to their
structure. The structure of the elements vary from metallic through giant molecular in the
metalloids to simple molecular structures in the non metals.

Chemistry of the Elements

1.2

REACTIONS OF THE ELEMENTS WITH CHLORINE, OXYGEN & WATER

Element
Na

Heat In Dry Chlorine

Very vigorous reaction. In the process:
Na+Cl- is formed.

Mg

Vigorous reaction. In the process: Mg+Clis formed.

Al

Vigorous reaction. In the process Al2Cl6 is

formed.

Si

Slow reaction. In the process: SiCl4 is

formed.

Slow reaction. In the process: PCl + PCl5

are formed.

Slow reaction. In the process: SCl2 + S2Cl2

are formed.

Cl

No reaction.

Ar

No reaction.

TABLE 1.6 Reactions Of Period Three With Dry Chlorine

Element
Na

Heat In Dry Oxygen

Very vigorous reaction. In the process: (Na+)2O2- +
(Na+)2O22- are formed.

Mg
Al

Vigorous reaction. In the process: Mg2+O2- is formed.

Vigorous reaction. In the process (Al3+)2(O2-)3 is
formed.

Si

Slow reaction. In the process: SiO2 is formed.

Vigorous reaction. In the process: P2O3 + P2O5 are

formed.

Slow reaction. In the process: SO2 is formed.

Cl

No reaction.

Ar

No reaction.

TABLE 1.7 Reactions Of Period Three With Dry Oxygen

Chemistry of the Elements

Element
Na

Addition Of Water
Very vigorous reaction. Na + H2O

H2

+ NaOH.
Mg

Weak reaction.

Al

No reaction.

Si

No reaction.

No reaction.

No reaction.

Cl

Slow reaction. Cl2 + H2O

H+ +Cl- +

O 2.
Ar

No reaction.

TABLE 1.8 Reactions Of Period Three With Hydrogen Oxide (Water)

Elements
Na

Heat In Dry Chlorine

Very Vigorous reaction
forming :

Heat In Dry Oxygen

Very vigorous reaction gives:
(Na+)2O2- + (Na+)2O2-2

Na+Cl-

Addition Of Water
Very vigorous
reaction.
Na + H2O H2 +
NaOH

Mg

Vigorous reaction
forming:

Vigorous reaction givies:

Weak reaction.

Mg2+O2-

Mg2+(Cl-)2
Al

Vigorous reaction
forming:

Vigorous reaction gives:

(Al )2 (O )3
3+

2-

Al2Cl6
Si

Slow reaction gives:

SiCl4

Slow reaction gives:

Pcl3 + PCl5

Slow reaction gives:

SiO2
Vigorous reaction gives:
P2O3 and P2O5

Chemistry of the Elements

S

Slow reaction gives:

Slow reaction gives:

SCl2 + S2Cl2
Cl

No reaction.

SO2
No reaction.

Cl2 + H2O HClO

HClO H+ + Cl- +
O2

Ar

No reaction.

No reaction.

TABLE 1.9 Reactions Of Period Three With Dry Chlorine, Dry Oxygen & Water.

RELATING THE PROPERTIES OF ELEMENTS TO THEIR STRUCTURE

Metals usually have high melting points, boiling points, heats of fusion and vaporization. These
high values suggest that there are strong forces between the separate atoms in the metal. In metals
the outer shell electrons move randomly and overlap throughout a lattice of regularly spaced
positive ions (or cation). The cations are often described as floating in a sea of mobile electrons.
In the metal lattice each positively charged ion is attracted to the sea or cloud of negative
electrons. The electrostatic attractions bind the entire crystal together as a single unit.
Moving from sodium (1 e-) through magnesium (2 e-) to aluminum (3 e-) in the outer shell, the
bonding gets gradually stronger, hence melting point, boiling point, etc gets stronger. The
stronger bonding from Na Mg Al means that the atoms are pulled closer together in Mg
than in Na and even closer in Al. This explains the increasing density.
STRUCTURE OF THE METALLOIDS (B, C, Si) GIANT MOLECULAR
Each atom can be imagined to be situated at the center of a regular tetrahedron (diamond, silicon)
strongly bonded by covalent bonds to four other atoms. Each tetrahedron is in turn linked to
another tetrahedron until a massive network of a gigantic structure is formed. Because of the
strong covalent bonds holding each atom tightly in the crystal it is difficult to break an atom away
from the lattice. Thus these elements have high melting points and boiling points. The electrons
within the covalent bonds are held much more tightly in these elements than metals and
consequently their thermal and electrical conductivities are lower.
SIMPLE MOLECULAR STRUCTURE
All the non metals in Periods 3 and 2 (except diamond) form simple molecular structures. They
form small molecules e.g. N2, O2, F2, Ne, P4, S8, Cl2 and Ar. The atoms are linked to form
covalent bonds within molecules or atoms and these structures are held by weak Van der waals
forces. The molecules are separated easily and so their melting points and boiling points are low.
Their densities are low and they have high molar volumes.

1.3

OXIDATION STATES OF THE OXIDES, CHLORIDES AND HYDRIDES

Element

Oxides

Chlorides

Hydrides

Na

+1

+1

NaH (-1)

Chemistry of the Elements

Mg

+2

+2

MgH2 (-2)

Al

+3

+3

AlH3 (-3)

Si

+4

+4

SiH4 (-4)

+3 , +5

+3 , +5

PH3 (-3)

+6 , +4

+1 , +2 ,

H2S (+2)

+4
Cl

+1 , +3 , +

-1

HCl (+1)

5 , +7
Ar

TABLE 1.10 Oxidation States Of Period Three

1.4

REACTIONS OF THE OXIDES & CHLORIDES OF THE ELEMENTS WITH WATER

REACTION OF THE CHLORIDES OF THE ELEMENTS WITH WATER

NaCl

(s)

MgCl2

(s)

AlCl3

(s)

SiCl4

(l)

PCl3 , PCl5

(l)

SCl2 , S2Cl2

Cl2

(g)

(l)

Dissolves to

Dissolves to

Hydrolyses

Hydrolyses

Hydrolyses to

Hydrolyses

Partially

give

give

to give:

to give:

give:

to give:

hydrolyses to

aqueous

aqueous

ions:

ions:

give:
Al(OH)5 +
3H

Na+

(aq)
(aq)

, C-

Mg2+

(aq)

2Cl-

(aq)

(aq)

+ 3Cl-

(aq)

SiO2
4H

(s)

PCl3

S(s) + H+

(aq)

H3PO4 (aq)

+ Cl

4Cl-

(aq)

+ 3H+

(aq)

3Cl-

(aq)

H3PO4 (aq)

TABLE 1.11 Reactions Of Period Threes Chlorides With Water

(aq)

5Cl-

(aq)

(aq)

(aq)

HClO

(aq)

H+

+ Cl-

(aq)

(aq)

PCl5
+ 3H+

Chemistry of the Elements

1.5

ACID / BASE BEHAVIOUR OF THE OXIDES AND HYDROXIDES

Na2O

MgO

Al2O3

Ionic

Ionic

Ionic With

SiO2

P2O3

SO2 , SO3

Macromolecular Macromolecular Molecular

Covalent

Cl2O7
Molecular

Covalent

Covalent

Covalent

Covalent

Acidic

Acidic

Strongly

Strongly

Acidic

Acidic

Character
Basic

Basic

Amphoteric

Na2O

Cl2O5 (g) +

+ H 2O

H 2O

H2

2HClO

(l)

cf
(aq)

NaOH
TABLE 1.12 The Oxides Of Period Three

Amphoteric Oxides
Al2O3

+ NaOH

NaAl(OH)4

Al2O3

+ 6HCl

Al2Cl6

+ 3H2O

To the left of the periods the oxides give hydroxides and to the left they give acids.

NaOH

Mg(OH)2

Al(OH)3

H2SiO3

H3PIO4

H2SO4

HClO4

Strong

Weak

Weak

Weak

Weak

Strong

Strong

Base
Base
TABLE 1.13
The Acids And Bases Of Period Three

Base

Acid

Acid

Acid

Acid

Chemistry of the Elements

NaCl

Na+Cl-

MgCl2

Mg2+(Cl-)2

Ionic
Essentially Ionic

Cl
AlCl3

Al

Planar

Cl

Cl
Cl

SiCL4

Si
Tetrahedral
Cl

Cl
Cl
..

PCl3

Pyramidal

Cl

Cl
Cl
..

SiCl2

..

Si
Cl

Cl2

Cl

FIGURE 1.2 Shapes Of The Chlorides In Period Three

Triangular
Cl
Cl

Linear

Chemistry of the Elements

1.6

CHEMICAL BONDING
DIAGONAL RELATIONSHIP
The metals that show diagonal relationships are:
Lithium & Magnesium
Beryllium & Aluminum
Boron & Silicon
Non metallic nature increases
Metallic

across.

nature
increase

Both metallic and non

metallic nature increase. Each

tends to cancel the effects of

downwa
the other.
FIGURE 1.3 Metallicity
rds. Of The Elements

COMPARISON OF THE ELEMENTS: LITHIUM AND MAGNESIUM

CO32-

Like MgCO3, Li2CO3 is decomposed by heat (the other

group 1 carbonates do not decompose). Both carbonates are
insoluble (the other group 1 carbonates are soluble).

Cl-

Both chlorides are hydrated. LiCl2.6H2O, MgCl2.6H2O (the

other group 1 chlorides are not hydrated).

O2-

Both give their normal oxides; Li2O, MgO when they burn.
The other group one elements give peroxides, e.g. N2O2.

Hydration

Both Li+ and Mg2+ ions are heavily hydrated in solution

(they are both dense centres of charges).

COMPARISON OF THE ELEMENTS: BERYLLIUM AND ALUMINIUM

With HNO3

Both metals are rendered passive and will not dissolve.

Weak Alkali

Both dissolve giving off hydrogen.

Amphoteric
Nature

Both metals are Amphoteric (react with both acid and

alkali).

O2-

Both BeO and Al2O3 are amphoteric.

Cl-

Both BeCl2 and AlCl3 are electron deficient. Both acts as

Lewis Acids.

Chemistry of the Elements

COMPARISON OF ELEMENTS: BORON AND SILICON

Hydrides

Both give a wide variety of unstable hydride: the borons

and silanes. Examples: BH4, B2H6, SiH4, Si2H6.

Oxides

Both are weakly acidic. Examples: Be2O3

And SiO2
H2SiO3.

Cl-

Both BCl3 and SiCl4 are volatile and will undergo

hydrolyses to give an acidic solution. Examples:
SiCl4 + 2H2O
2BCl3 + 3H2O

SiO2 + 4HCl
B2O3 + 6HCl

H3BO3