Trends in Atomic Radius

Note: You will find atomic radius covered in detail in another part of this site. If you
choose to follow this link, use the BACK button on your browser to return quickly to
this page.

You can see that the atomic radius increases as you go down the Group.
Explaining the increase in atomic radius
The radius of an atom is governed by
the number of layers of electrons around the nucleus
the pull the outer electrons feel from the nucleus.
Compare fluorine and chlorine:
F

2,7

Cl

2,8,7

In each case, the outer electrons feel a net pull of 7+ from the nucleus. The positive
charge on the nucleus is cut down by the negativeness of the inner electrons.

This is equally true for all the other atoms in Group 7. The outer electrons always
feel a net pull of 7+ from the centre.
The only factor which is going to affect the size of the atom is therefore the number
of layers of inner electrons which have to be fitted in around the atom. Obviously,
the more layers of electrons you have, the more space they will take up - electrons
repel each other. That means that the atoms are bound to get bigger as you go
down the Group.
Trends in Electronegativity
Electronegativity is a measure of the tendency of an atom to attract a bonding pair
of electrons. It is usually measured on the Pauling scale, on which the most
electronegative element (fluorine) is given an electronegativity of 4.0.
Note: You will find electronegativity covered in detail in another part of this site. If
you choose to follow this link, use the BACK button on your browser to return quickly
to this page.

Notice that electronegativity falls as you go down the Group. The atoms become less
good at attracting bonding pairs of electrons.
Explaining the decrease in electronegativity

This is easily shown using simple dots-and-crosses diagrams for hydrogen fluoride
and hydrogen chloride.

The bonding pair of electrons between the hydrogen and the halogen feels the same
net pull of 7+ from both the fluorine and the chlorine. (This is exactly the same sort
of argument as you have seen in the atomic radius section above.) However, in the
chlorine case, the nucleus is further away from that bonding pair. That means that it
won't be as strongly attracted as in the fluorine case.
The larger pull from the closer fluorine nucleus is why fluorine is more
electronegative than chlorine is.
Summarising the trend down the Group
As the halogen atoms get bigger, any bonding pair gets further and further away
from the halogen nucleus, and so is less strongly attracted towards it. In other
words, as you go down the Group, the elements become less electronegative.
Trends in First Electron Affinity
Defining first electron affinity
The first electron affinity is the energy released when 1 mole of gaseous atoms each
acquire an electron to form 1 mole of gaseous 1- ions.
This is more easily seen in symbol terms.
It is the energy released (per mole of X) when this change happens.
First electron affinities have negative values. For example, the first electron affinity
of chlorine is -349 kJ mol-1. By convention, the negative sign shows a release of
energy.
The first electron affinities of the Group 7 elements

Notice that the trend down the Group isn't tidy. The tendency is for the electron
affinities to decrease (in the sense that less heat is given out), but the fluorine value
is out of line.
The electron affinity is a measure of the attraction between the incoming electron
and the nucleus. The higher the attraction, the higher the electron affinity.

In the bigger atom, the attraction from the more positive nucleus is offset by the
additional screening electrons, so each incoming electron feels the effect of a net 7+
charges from the centre - exactly as when you are thinking about atomic radius or
electronegativity.
As the atom gets bigger, the incoming electron is further from the nucleus and so
feels less attraction. The electron affinity therefore falls as you go down the Group.
But what about fluorine? That is a very small atom, with the incoming electron quite
close to the nucleus. Why isn't its electron affinity bigger than chlorine's?
There is another effect operating. When the new electron comes into the atom, it is
entering a region of space already very negatively charged because of the existing
electrons. There is bound to be some repulsion, offsetting some of the attraction
from the nucleus.
In the case of fluorine, because the atom is very small, the existing electron density
is very high. That means that the extra repulsion is particularly great and lessens
the attraction from the nucleus enough to lower the electron affinity below that of
chlorine.

Trends in Melting Point and Boiling Point

You will see that both melting points and boiling points rise as you go down the
Group.
If you explore the graphs, you will find that fluorine and chlorine are gases at room
temperature, bromine is a liquid and iodine a solid. Nothing very surprising there!
Explaining the trends in melting point and boiling point
All of the halogens exist as diatomic molecules - F2, Cl2, and so on. The
intermolecular attractions between one molecule and its neighbours are van der
Waals dispersion forces.
As the molecules get bigger there are obviously more electrons which can move
around and set up the temporary dipoles which create these attractions.
The stronger intermolecular attractions as the molecules get bigger means that you
have to supply more heat energy to turn them into either a liquid or a gas - and so
their melting and boiling points rise.
Solubilities
Solubility in water
Fluorine reacts violently with water to give hydrogen fluoride gas (or a solution of
hydrofluoric acid) and a mixture of oxygen and ozone. So thinking about its solubility
is pointless. Chlorine, bromine and iodine all dissolve in water to some extent, but
there is no pattern in this. The following table shows the solubility of the three
elements in water at 25C.

(mol dm-3) solubility

chlorine

0.091

bromine

0.21

iodine 0.0013
Chlorine solution in water is pale green. Bromine solution in water is anything from
yellow to dark orange-red depending on how concentrated it is. Iodine solution in
water is very pale brown.
Chlorine reacts with water to some extent to give a mixture of hydrochloric acid and
chloric(I) acid - also known as hypochlorous acid. The reaction is reversible, and at
any one time only about a third of the chlorine molecules have actually reacted.

You will sometimes find the chloric(I) acid written as HOCl. That represents the way
the atoms are actually joined together.
Bromine and iodine do something similar, but to a much lesser extent. In both cases,
about 99.5% of the halogen remains as unreacted molecules.
The solubility of iodine in potassium iodide solution
Although iodine is only faintly soluble in water, it does dissolve freely in potassium
iodide solution to give a dark red-brown solution. There is a reversible reaction
between iodine molecules and iodide ions to give I3- ions. These are responsible for
the colour.
In the lab, iodine is often produced by oxidation of a solution containing iodide ions,
so this colour is actually quite familiar. As long as there are any excess iodide ions
present, the iodine will react with them to make the I3- ions. Once the iodide ions
have all reacted, the iodine is precipitated as a dark grey solid, because there isn't
anything left for it to react with to keep it in solution.
Solubility in hexane
The halogens are much more soluble in organic solvents like hexane than they are in
water. Both hexane and the halogens are non-polar molecules attracted to each
other by van der Waals dispersion forces.
That means that the attractions broken (between hexane molecules and between
halogen molecules) are similar to the new attractions made when the two
substances mix.
The colours of the solutions formed are much what you would expect. Solutions of
iodine in organic solvents tend to be pinky-purple colour.
Bond enthalpies (bond energies or bond strengths)

Bond enthalpy is the heat needed to break one mole of a covalent bond to produce
individual atoms, starting from the original substance in the gas state, and ending
with gaseous atoms.
So for chlorine, Cl2(g), it is the heat energy needed to carry out this change per
mole of bond:

For bromine, the reaction is still from gaseous bromine molecules to separate
gaseous atoms.

Bond enthalpy in the halogens, X2(g)

A covalent bond works because the bonding pair is attracted to both the nuclei at
either side of it. It is that attraction which holds the molecule together. The size of
the attraction will depend, amongst other things, on the distance from the bonding
pair to the two nuclei.
As with all halogens, the bonding pair will feel a net pull of 7+ from both ends of the
bond - the charge on the nucleus offset by the inner electrons. That will still be the
same whatever the size of the halogen atoms.
As the atoms get bigger, the bonding pair gets further from the nuclei and so you
would expect the strength of the bond to fall.

So . . . are the actual bond enthalpies in line with this prediction?

The bond enthalpies of the Cl-Cl, Br-Br and I-I bonds fall just as you would expect,
but the F-F bond is way out of line!
Because fluorine atoms are so small, you might expect a very strong bond - in fact,
it is remarkably weak. There must be another factor at work as well.
As well as the bonding pair of electrons between the two atoms, each atom has 3
non-bonding pairs of electrons in the outer level - lone pairs. Where the bond gets
very short (as in F-F), the lone pairs on the two atoms get close enough together to
set up a significant amount of repulsion.

In the case of fluorine, this repulsion is great enough to counteract quite a lot of the
attraction between the bonding pair and the two nuclei. This obviously weakens the
bond.

Bond enthalpies in the hydrogen halides, HX(g)

Where the halogen atom is attached to a hydrogen atom, this effect doesn't happen.
There are no lone pairs on a hydrogen atom!

As the halogen atom gets bigger, the

bonding pair gets more and more distant from the nucleus. The attraction is less,
and the bond gets weaker - exactly what is shown by the data. There is nothing
complicated happening in this case.

This is important in the thermal stability of the hydrogen halides - how easily they
are broken up into hydrogen and the halogen on heating.
Hydrogen fluoride and hydrogen chloride are very stable to heat. They don't split up
into hydrogen and fluorine or chlorine again if heated to any normal lab
temperature.
Hydrogen bromide splits slightly into hydrogen and bromine on heating, and
hydrogen iodide splits to an even greater extent.
As the bonds get weaker, they are more easily broken.
Note: Breaking the hydrogen-halogen bond is only one of the steps in the overall
reaction, of course. You don't end up with hydrogen atoms and halogen atoms - you
get diatomic molecules, H2 and X2. If you have done some energetics calculations,
it would be a useful exercise to use bond enthalpies and atomisation enthalpies to
calculate the overall enthalpy changes for the decomposition of the hydrogen
halides.
(Remember that bond enthalpies only apply to substances in the gas state, and
bromine and iodine would end up as liquid and solid respectively. Using atomisation
enthalpies for the halogens avoids this problem. If you don't understand what I am
talking about, you don't yet have enough knowledge to be able to do this.)