Chemical Periodicity (REVISED)

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Chemical Periodicity

Periodicity is the repetition of both physical and chemical properties of the


elements both across periods and down groups. This can coincide with repetition in
electronic configurations.

There are two definitions of atomic radius:


1. Covalent Radius – half the distance between the nuclei of atoms of the same
element covalently bonded within the same molecule (most commonly
used).
2. Van der Waals Radius – half the distance between the nuclei of two atoms of
the same element from two different molecules (not chemically bonded).

The atomic radius decreases across period 3:


1. The nuclear charge increases, so the electrons are drawn closer to the
nucleus.
2. There is no additional shielding for the increase in nuclear charge.

There is a general increase in first I.E. as atomic number increases because


1. The nuclear charge increases, due to increase in number of protons and
electrons.
2. The radius of atom decreases with increasing atomic number, hence more
energy required to remove outer electrons.

Electrical conductivity across period 3:


1. This increases from Na to Al, because the number of delocalised electrons
able to carry current increases, thus increasing the ability to conduct
electricity.
2. The elements Si to Ar have close to zero electrical conductivity, because
they bond covalently, so the electrons are not free to conduct electricity.

Melting and boiling points across period 3:


1. These are linked to the bond strength and structure of the elements.
2. Na to Al are metals – the melting and boiling points increase because the
nuclear charge and the size of the atoms increase, so the attraction between
them is greater, and more energy is needed to melt or to boil them.
3. Si is macromolecular – it has a great deal of very strong covalent bonds,
which require a lot of energy to break. It therefore has very high melting and
boiling points.

Chemistry Notes by Azhaar Miyanji ©


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4. P to Cl are molecular – the melting and boiling points depend on the Van
der Waals forces between the molecules. The melting and boiling points are
highest in sulphur (S8), followed by phosphorus (P4) followed by chlorine
(Cl2), as the bigger molecules are most polarisable and thus have stronger
intermolecular forces. All the melting and boiling points are very low
though, as Van der Waals forces are easily broken.
5. Ar is monatomic – it has very little Van der Waals forces between atoms,
and so its melting and boiling points are extremely low.

The atomic radius increases down group II:


1. The number of electron shells increases, so the outermost electron is further
away from the nucleus and the radius is bigger.
2. Although the nuclear charge increases, there is more shielding from
complete inner shells, so the radius will still increase.

Electronegativity decreases down group II:


1. The electrons are further from the nucleus, and are shielded by complete
inner electron shells as you go down the group, so the attraction for the
electrons decreases, even though the nuclear charge increases.
2. The electronegativity will therefore decrease, because the electrons aren’t as
strongly attracted to the element.
3. Beryllium forms a very small highly charged ion, and so has a great
attraction for electrons from a larger negative ion, forming essentially a
covalent bond (the electron density is concentrated between the ions). Going
down the group, the ions get larger, and so the charge is less concentrated
and the attraction for electrons is less, so the electronegativity decreases.

Melting points down group II:


1. All of the group are metals with high melting points.
2. The overall trend is a decrease in melting point, because the atoms get
bigger and have more shielding, even though the nuclear charge increases,
so the attraction for the delocalised electrons is less. This means that less
energy is required to separate the atoms, and thus the melting point
decreases.
3. Magnesium has a lower than expected melting point, due to a difference in
its metallic structure meaning that the ions can’t pack together as closely.

The reactivity of elements with water increases down group II:


1. Beryllium does not react with cold water or steam.

Chemistry Notes by Azhaar Miyanji ©


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2. Magnesium reacts with steam, and very slowly with cold water:
Mg(s) + H2O (g) → MgO (s) + H2(g)
3. Calcium, strontium and barium all react with cold water, and the reactivity
increases going down the group, producing solutions of the metal hydroxide.
For calcium:
Ca(s) + 2H2O (l) → Ca(OH)2 (aq) + 2H2(g)

The solubility of group II hydroxides and sulphates:


1. Hydroxides increase in solubility down the group. Barium hydroxide
produces strongly alkaline solutions:
Ba(OH)2(s)+aq→Ba2+(aq)+2OH-(aq)
2. Sulphates decrease in solubility down the group.
3. Barium sulphate is insoluble, and is used as a test for sulphate ions – dilute
acid (HCL orHNO3) and a solution of barium ions (from BaCl2 or
Ba(NO3)2) are added, giving a white precipitate in the presence of sulphate
ions: Ba (aq) SO (aq) BaSO4 (s) d. The acid is added to remove carbonate
ions which would form barium carbonate (also insoluble):
2H (aq) CO (aq) → CO2 (g) + H2O(l)

The atypical nature of beryllium:


1. The chlorides of other group II elements are ionic, but for beryllium, it forms
a linear covalent molecule. This is because of the high-density charge on the
small beryllium ion, which attracts the electron cloud between the two ions,
creating a covalent bond. BeCl2 is a poor conductor of electricity and is
soluble in organic solvents, unlike ionic compounds.
2. The other group II element’s hydroxides are basic, i.e. they dissolve in acids
but not inbases:
Mg(OH) (s) 2H (aq) 4H O(l) → [Mg(H O) ]2 (aq)
3. Beryllium hydroxide dissolves in both acids and bases – i.e. it is amphoteric:

Be(OH) (s) 2H (aq) 2H O(l) → [Be(H O) ]2 (aq)


Be(OH) (s) 2OH (aq) → [Be(OH) ]2 (aq)

4. As the beryllium ion is so small, only four coordinate bonds can fit around
it. It therefore has a maximum coordination number of 4. Other elements in
group II have a maximum coordination number of 6.
5. Beryllium chloride molecules can bond together via coordinate bonds to
form dimers. In this case beryllium shows a coordination number of 3.

Chemistry Notes by Azhaar Miyanji ©

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