Period 3: Sodium to Argon

Table of Atomic Radii

Atomic radius
Element Proton number Symbol
(nm)
sodium 11 Na 0.191
magnesium 12 Mg 0.160
aluminium 13 Al 0.130
silicon 14 Si 0.118
phosphorus 15 P 0.110
sulphur 16 S 0.102
chlorine 17 Cl 0.099
argon 18 Ar 0.095
Graph of physical data
Explanation
• Going across Period 3:
• the number of protons in the nucleus increases so ...
• the nuclear charge increases ...
• there are more electrons, but the increase in shielding is negligible because each
extra electron enters the same principal energy level ...
• therefore the force of attraction between the nucleus and the electrons
increases ...
• so the atomic radius decreases.
• As the number of electrons in each atom increases going across Period 3, you
might expect the atomic radius to increase. This does not happen, because the
number of protons also increases and there is relatively little extra shielding
from electrons in the same principal energy level.
Ionic radii
• As we move across from sodium to aluminium, the ionic radius
decreases. This is because the ratio of protons to electrons increases
as the metal loses its outer shell of electrons.
• As we move from phosphorus to chlorine, the ionic radius of the non-
metallic ion is larger than the corresponding atom. This is because
electrons are being added to valence shell which results in more
electron repulsion
• As the nuclear charge increases, the ionic radius of the negative ions
decreases.
Table

Na+ Mg2+ Al3+ P3- S2- Cl-

no of
11 12 13 15 16 17
protons

electronic
structure 2,8 2,8 2,8 2,8,8 2,8,8 2,8,8
of ion

ionic
radius 0.102 0.072 0.054 (0.212) 0.184 0.181
(nm)
Ionisation energy
• First ionisation energy generally increases going across Period 3.

• The first ionisation energy drops between magnesium and

aluminium before increasing again.

• The first ionisation energy drops between phosphorus and

sulphur before increasing again.
Table

First ionisation
Element Proton number Symbol
energy (kJ/mol)
sodium 11 Na 496
magnesium 12 Mg 738
aluminium 13 Al 578
silicon 14 Si 789
phosphorus 15 P 1012
sulphur 16 S 1000
chlorine 17 Cl 1251
argon 18 Ar 1521
Graph
• General increase across the period
• The first ionisation energy is the enthalpy change when one mole of gaseous
atoms forms one mole of gaseous ions with a single positive charge. It is an
endothermic process, i.e. positive
• Going across Period 3:
• there are more protons in each nucleus so the nuclear charge in each element
increases ...
• therefore the force of attraction between the nucleus and outer electron is
increased, and ...
• there is a negligible increase in shielding because each successive electron enters
the same energy level ...
• so more energy is needed to remove the outer electron.
• Magnesium to aluminium
• Look at their electronic configurations:
• Magnesium: 1s2 2s2 2p6 3s2 ... and ... aluminium: 1s2 2s2 2p6 3s2 3p1
• The outer electron in aluminium is in a p sub-level. This is higher in
energy than the outer electron in magnesium, which is in an s sub-
level, so less energy is needed to remove it.
• Phosphorus to sulphur
• Look at their electronic configurations:
• Phosphorus: 1s2 2s2 2p6 3s2 3p3 ... and ... sulphur: 1s2 2s2 2p6 3s2 3p4
• It's not immediately obvious what's going on until we look at the
arrangements of the electrons:
• The 3p electrons in phosphorus are all unpaired. In sulphur, two of
the 3p electrons are paired. There is some repulsion between paired
electrons in the same sub-level. This reduces the force of their
attraction to the nucleus, so less energy is needed to remove one of
these paired electrons than is needed to remove an unpaired electron
from phosphorus.
Electronegativity
• Electronegativity increases going across Period 3
Table
Electronega
Proton tivity
Element Symbol
number (scale 0 to
4)
sodium 11 Na 0.9

magnesium 12 Mg 1.2

aluminium 13 Al 1.5
silicon 14 Si 1.8

phosphorus 15 P 2.1

sulphur 16 S 2.5
chlorine 17 Cl 3.0
Graph
Explanation of trend
• Electronegativity is the relative ability of an atom to attract the bonding electron pair in a covalent bond (to withdraw
electron density). It cannot be measured directly. In the Pauling electronegativity index, the most electronegative element
(fluorine) is given an electronegativity value of 4. Note that there are no values for the noble gases (Group 0) as they do
not usually form covalent bonds.
Going across Period 3:
• the nuclear charge increases ...
• the atomic radius decreases ...
• there are more electrons, but the increase in shielding is negligible because each extra electron enters the same principal
energy level ...
• so electrons will be more strongly attracted to the nucleus.
• Remember that ionisation energies are all endothermic processes (i.e. energy is needed to remove electrons), so atoms
with low electronegativities do not have a tendency to lose electrons. They just have a weaker tendency than other atoms
to attract the bonding electron pair in a covalent bond.
• In Period 3, sodium with 11 protons is the least electronegative element, and chlorine with 17 protons is the most
electronegative element. You might expect argon (with 18 electrons) to be the most electronegative element in Period 3,
but its outer energy levels are full. Therefore, it does not form covalent bonds with other atoms, so it is given an
electronegativity value of zero.
Melting and Boiling Points
• Melting points generally increase going from sodium to silicon, then
decrease going to argon (with a “bump” at sulphur).
• Boiling points generally increase going from sodium to aluminium,
then decrease to argon (again with a “bump” at sulphur).
Table
Melting Boiling
Proton
Element Symbol point point
number
(K) (K)
sodium 11 Na 371 1156
magnesi
12 Mg 922 1380
um
aluminiu
13 Al 933 2740
m
silicon 14 Si 1683 2628
phospho
15 P 317 553
rus
sulphur 16 S 392 718
chlorine 17 Cl 172 238
argon 18 Ar 84 87
Graph
Explanation of trends
• Melting
• When a substance melts, some of the attractive forces holding the
particles together are broken or loosened so that the particles can
move freely around each other but are still close together. The
stronger these forces are, the more energy is needed to overcome
them and the higher the melting temperature.
• Boiling
• When a substance boils, most of the remaining attractive forces are
broken so the particles can move freely and far apart. The stronger
the attractive forces are, the more energy is needed to overcome
them and the higher the boiling temperature.
• Sodium, magnesium and aluminium
• Sodium, magnesium and aluminium are all metals. They
have metallic bonding, in which positive metal ions are attracted to
delocalised electrons. Going from sodium to aluminium:
• the charge on the metal ions increases from +1 to +3 (with
magnesium at +2) ...
• the number of delocalised electrons increases ...
• so the strength of the metallic bonding increases and ...
• the melting points and boiling points increase.
• Silicon
• Silicon is a metalloid (an element with some of the properties of
metals and some of the properties of non-metals). Silicon has giant
covalent bonding. It has a giant lattice structure similar to that
of diamond, in which each silicon atom is covalently-bonded to four
other silicon atoms in a tetrahedral arrangement. This extends in
three dimensions to form a giant molecule or macromolecule.
• Silicon has a very high melting point and boiling point because:
• all the silicon atoms are held together by strong covalent bonds ...
• which need a very large amount of energy to be broken.
• Phosphorus, sulphur, chlorine and argon
• These are all non-metals, and they exist as small, separate molecules. Phosphorus, sulphur and
chlorine exist as simple molecules, with strong covalent bonds between their atoms. Argon exists
as separate atoms (it is monatomic).
• Their melting and boiling points are very low because:
• when these four substances melt or boil, it is the van der Waals’ forces between the molecules
which are broken ...
• which are very weak bonds ...
• so little energy is needed to overcome them.
• Sulphur has a higher melting point and boiling point than the other three because:
• phosphorus exists as P4 molecules ...
• sulphur exists as S8 molecules ...
• chlorine exists as Cl2 molecules ...
• argon exists individual Ar atoms ...
• the strength of the van der Waals’ forces decreases as the size of the molecule decreases ...
• so the melting points and boiling points decrease in the order S8 > P4 > Cl2 > Ar
Electrical conductivity
• Electrical conductivity increases going across Period 3 from sodium to
aluminium, then decreases to silicon. The remaining elements have
negligible conductivity.
Table
Relative
electrical
Proton
Element Symbol conductivi
number
ty
(Al = 1)
sodium 11 Na 0.55

magnesium 12 Mg 0.61

aluminium 13 Al 1.00
silicon 14 Si 0.10

phosphorus 15 P 0

sulphur 16 S 0
chlorine 17 Cl 0
argon 18 Ar 0
Graph
Explanation of trend
• For an element to conduct electricity, it must contain electrons that
are free to move. In general, metals are good conductors of electricity
and non-metals are poor conductors of electricity.
• Sodium, magnesium and aluminium
• Sodium, magnesium and aluminium are all metals. They
have metallic bonding, in which positive metal ions are attracted to
delocalised electrons. The delocalised electrons are free to move and
carry charge. Going from sodium to aluminium:
• the number of delocalised electrons increases ...
• there are more electrons which can move and carry charge ...
• so the electrical conductivity increases.
• Silicon
• Silicon is a metalloid (an element with some of the properties of metals
and some of the properties of non-metals). Silicon has giant covalent
bonding. It has a giant lattice structure similar to that of diamond, in which
each silicon atom is covalently-bonded to four other silicon atoms in a
tetrahedral arrangement. This extends in three dimensions to form a giant
molecule or macromolecule.
• Silicon is called a semiconductor because:
• the four outer electrons in each atom are held strongly in covalent bonds ...
• few electrons have enough energy at room temperature to enter the
higher energy levels ...
• so there are few delocalised electrons and silicon is a poor conductor ... but
...
• at higher temperatures more electrons are promoted to the higher energy
levels ...
• so there are more delocalised electrons to move and carry charge.
• Non-metals
• The remaining elements in Period 3 do not conduct electricity:
• in phosphorus, sulphur and chlorine, the outer electrons are not free
to move and carry charge because they are held strongly in covalent
bonds ...
• in argon (which exists as single atoms) the outer electrons are not
free to move and carry charge because they are held strongly in a
stable third energy level.
Density
Explanation of Trend
• The density increases from sodium to aluminium as the atomic radii
decrease and the bonding gets stronger with 1 ==> 3 bonding
electrons (delocalised outer valency electrons in the metal
lattice). However, they are relatively low densities compared to most
metals.
• Silicon, phosphorus and sulfur have a low densities, typical of non–
metallic covalent solids.
• Chlorine and argon are small covalent molecules and have very low
densities being gaseous at room temperature because only weak
intermolecular forces act between them.
Reaction of elements with oxygen, chlorine
and water
Reactions with water
Sodium
• Sodium has a very exothermic reaction with cold water producing
hydrogen and a colourless solution of sodium hydroxide.
Magnesium
• Magnesium has a very slight reaction with cold water, but burns in steam.
• A very clean coil of magnesium dropped into cold water eventually gets
covered in small bubbles of hydrogen which float it to the surface.
Magnesium hydroxide is formed as a very thin layer on the magnesium and
this tends to stop the reaction.
• Magnesium burns in steam with its typical white flame to produce white
magnesium oxide and hydrogen.
Aluminium
• Aluminium powder heated in steam produces hydrogen and aluminium oxide.
The reaction is relatively slow because of the existing strong aluminium oxide
layer on the metal, and the build-up of even more oxide during the reaction.
Silicon
• There is a fair amount of disagreement in the books and on the web about what
silicon does with water or steam. The truth seems to depend on the precise form
of silicon you are using.
• The common shiny grey lumps of silicon with a rather metal-like appearance are
fairly unreactive. Most sources suggest that this form of silicon will react with
steam at red heat to produce silicon dioxide and hydrogen.
Phosphorus and sulphur
• These have no reaction with water.
Chlorine
• Chlorine dissolves in water to some extent to give a green solution. A
reversible reaction takes place to produce a mixture of hydrochloric
acid and chloric(I) acid (hypochlorous acid).
• In the presence of sunlight, the chloric(I) acid slowly decomposes to
produce more hydrochloric acid, releasing oxygen gas, and you may
come across an equation showing the overall change:
Argon
• There is no reaction between argon and water.

Reactions with chlorine

Sodium
• Sodium burns in chlorine with a bright orange flame. White solid
sodium chloride is produced.
• Magnesium
• Magnesium burns with its usual intense white flame to give white
magnesium chloride.
Aluminium
• Aluminium is often reacted with chlorine by passing dry chlorine over
aluminium foil heated in a long tube. The aluminium burns in the
stream of chlorine to produce very pale yellow aluminium chloride.
This sublimes (turns straight from solid to vapour and back again) and
collects further down the tube where it is cooler.
• Silicon
• If chlorine is passed over silicon powder heated in a tube, it reacts to
produce silicon tetrachloride. This is a colourless liquid which vaporises
and can be condensed further along the apparatus.
Phosphorus
• White phosphorus burns spontaneously in chlorine to produce a
mixture of two chlorides, phosphorus(III) chloride and phosphorus(V)
chloride (phosphorus trichloride and phosphorus pentachloride).
• Phosphorus(III) chloride is a colourless fuming liquid.
• Phosphorus(V) chloride is an off-white (going towards yellow) solid.
Sulphur
• If a stream of chlorine is passed over some heated sulphur, it reacts to
form an orange, evil-smelling liquid, disulphur dichloride, S2Cl2.
• Chlorine and argon
• It obviously doesn't make sense to talk about chlorine reacting with
itself, and argon doesn't react with chlorine.
• Reactions with oxygen
• Sodium
• Sodium burns in oxygen with an orange flame to produce a white
solid mixture of sodium oxide and sodium peroxide.
• Magnesium
• Magnesium burns in oxygen with an intense white flame to give white
solid magnesium oxide.
• Aluminium
• Aluminium will burn in oxygen if it is powdered, otherwise the strong
oxide layer on the aluminium tends to inhibit the reaction. If you
sprinkle aluminium powder into a Bunsen flame, you get white
sparkles. White aluminium oxide is formed.
Silicon
• Silicon will burn in oxygen if heated strongly enough. Silicon dioxide is
produced.
Phosphorus
• White phosphorus catches fire spontaneously in air, burning with a white
flame and producing clouds of white smoke - a mixture of phosphorus(III)
oxide and phosphorus(V) oxide.
• The proportions of these depend on the amount of oxygen available. In an
excess of oxygen, the product will be almost entirely phosphorus(V) oxide.
Sulphur
• Sulphur burns in air or oxygen on gentle heating with a pale blue flame. It
produces colourless sulphur dioxide gas.
Chlorine and argon
• Despite having several oxides, chlorine won't react directly with oxygen.
Argon doesn't react either.
The oxides we'll be looking at are:

Physical properties of the oxides

Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7

P4O6 SO2 Cl2O

• Oxides of elements in Period 3 all exist in positive oxidation states
because oxygen is more electronegative than any of these elements.
Oxide Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7

Max. +1 +2 +3 +4 +5 +6 +7
oxidation
state
• Oxidation state increases across the period because of the ability of
elements to use all electrons in their valence shells in bonding.
• Chlorides of Period 3 also exist in positive oxidation states because
chlorine is more electronegative than other elements in the period.
Chloride NaCl MgCl2 AlCl3 SiCl4 PCl5 SCl2

Max. +1 +2 +3 +4 +5 +2
oxidation
state
Bonding in chlorides and oxides
• This is related to electronegativity. The larger the difference, the more
likely it is that the oxide or chloride will be ionic.
• Na, Mg and Al form ionic oxides. The others are covalently bonded.
• Silicon dioxide has a giant covalent structure.
• Oxides of P, S and Cl have a simple molecular structure.
• Na and Mg chloride are ionic while aluminium chloride is covalently
bonded.
• Chlorides of Si, P and S have simple molecular structure.
Reactions of Period 3 Oxides and hydroxides
• Oxides of sodium and magnesium react with water to form hydroxides.
• They are basic solutions.
• They react with acids to form salt and water
• Aluminium oxide does not dissolve in water but reacts with acids and
alkalis. It is known as an amphoteric oxide because it reacts with both acid
and base.
• Silicon dioxide is insoluble in water but reacts with hot alkali. It is an acidic
oxide.
• Oxides of P, S and Cl are all acidic oxides. They react with water to form
acidic solutions and with alkalis to form salts.
Reactions of the chlorides of Period 3
• Chlorides of Na and Mg and hydrated aluminium chloride dissolve in
water because they are ionic.
• The chlorides of Si and P are hydrolysed by water to form acidic
solutions. Fumes of Hydrogen chloride are also released.
• The hydrolysis of Sulphur chloride is complex, several Sulphur
compounds including thionic acid are formed.