THE GROUP 7 ELEMENTS (THE HALOGENS)

Trends in Atomic Radius

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
Compare fluorine and chlorine:
• 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 negative
charge of the inner electrons
Compare fluorine and chlorine:
• 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.
Trends in Electronegativity
Trends in Electronegativity
• 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
• 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.
The first electron affinities of the Group 7
elements
• 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
The first electron affinities of the Group 7
elements
The first electron affinities of the Group 7
elements
• 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.
The first electron affinities of the Group 7
elements
• 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.
The first electron affinities of the Group 7
elements
• 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
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.
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.
Explaining the trends in melting point and
boiling point
• 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 25°C.
 solubility
(mol dm-3)
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:
Bond enthalpies
• 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.
Bond enthalpy
• 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.
Bond enthalpy
Bond enthalpy
• 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.
Bond enthalpy
• 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!
Bond enthalpies in the hydrogen halides, HX(g)

• 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.

• This is important in the thermal stability of the hydrogen halides -

how easily they are broken up into hydrogen and the halogen on
heating.
Bond enthalpies in the hydrogen halides, HX(g)

• 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

THE OXIDISING ABILITY OF THE
GROUP 7 ELEMENTS (THE HALOGENS)
• We are going to look at the reactions between one halogen (chlorine,
say) and the ions of another one (iodide ions, perhaps)
• The iodide ions will be in a solution of a salt like sodium or potassium
iodide. The sodium or potassium ions will be spectator ions, and are
completely irrelevant to the reaction.
• In the chlorine and iodide ion case, the reaction would be:
THE OXIDISING ABILITY OF THE
GROUP 7 ELEMENTS
• The iodide ions have lost electrons to form iodine molecules. They
have been oxidised.

• The chlorine molecules have gained electrons to form chloride ions.

They have been reduced.

• This is obviously a redox reaction in which chlorine is acting as an

oxidising agent.
Fluorine

• We'll have to exclude fluorine from this descriptive bit, because it is

too strong an oxidising agent. Fluorine oxidises water to oxygen and
so it is impossible to do simple solution reactions with it.
THE OXIDISING ABILITY OF THE
GROUP 7 ELEMENTS
• Chlorine, bromine and iodine

• In each case, a halogen higher in the Group can oxidise the ions of
one lower down. For example, chlorine can oxidise the bromide ions
(in, for example, potassium bromide solution) to bromine:
THE OXIDISING ABILITY OF THE
GROUP 7 ELEMENTS
• The bromine appears as an orange solution.

• As you have seen above, chlorine can also oxidise iodide ions (in, for
example, potassium iodide solution) to iodine:
THE OXIDISING ABILITY OF THE
GROUP 7 ELEMENTS
• The iodine appears either as a red solution if you are mean with the
amount of chlorine you use, or as a dark grey precipitate if the
chlorine is in excess.
THE OXIDISING ABILITY OF THE
GROUP 7 ELEMENTS
• Bromine can only oxidise iodide ions to iodine. It isn't a strong enough
oxidising agent to convert chloride ions into chlorine. (You have just
seen exactly the reverse of that happening.)

• A red solution of iodine is formed (see the note above) until the
bromine is in excess. Then you get a dark grey precipitate.
To summarise

• Oxidation is loss of electrons. Each of the elements (for example, chlorine)

could potentially take electrons from something else to make their ions
(e.g. Cl-). That means that they are all potentially oxidising agents.

• Fluorine is such a powerful oxidising agent that you can't reasonably do

solution reactions with it.

• Chlorine has the ability to take electrons from both bromide ions and
iodide ions. Bromine and iodine can't get those electrons back from the
chloride ions formed.
• That means that chlorine is a more powerful oxidising agent than
either bromine or iodine.

• Similarly bromine is a more powerful oxidising agent than iodine.

Bromine can remove electrons from iodide ions to give iodine - and
the iodine can't get them back from the bromide ions formed.

• This all means that oxidising ability falls as you go down the Group
Explaining the trend

• Whenever one of these halogens is involved in oxidising something in

solution, the halogen ends up as halide ions with water molecules
attached to them. Looking at all four of the common halogens:
• As you go down the Group, the ease with which these hydrated ions
are formed falls, and so the halogens become less good as oxidising
agents - less ready to take electrons from something else.

• The reason that the hydrated ions form less readily as you go down
the Group is a fairly complicated mixture of several factors.
The faulty explanation

• This is normally given for the trend in oxidising ability of chlorine, bromine and iodine, and goes like
this:

• How easily the element forms its ions depends on how strongly the new electrons are attracted. As
the atoms get bigger, the new electrons find themselves further from the nucleus, and more and
more screened from it by the inner electrons (offsetting the effect of the greater nuclear charge).
The bigger atoms are therefore less good at attracting new electrons and forming ions.

• That sounds reasonable! What's wrong with it?

• What we are describing is the trend in electron affinity as you go from chlorine to bromine to iodine.
Electron affinity tends to fall as you go down the Group. This is described in detail on another page.
• The snag comes if you try to expand the argument to include fluorine.
Fluorine has a much higher tendency to form its hydrated ion than
chlorine does. BUT . . . the tendency of the fluorine atom to gain an
electron is less than that of chlorine - as measured by its electron affinity!
That makes a nonsense of the whole argument.

• So, what is going wrong? The mistake is to look at only one part of a much
more complicated process. The argument about atoms accepting
electrons applies to isolated atoms in the gas state picking up electrons to
make isolated ions - also in the gas state. That's not what we should be
talking about.
• The halogen starts as diatomic molecules, X2 - which may be gas,
liquid or solid, depending on the halogen.

• These have to be split apart to make individual atoms.

• Those atoms each gain an electron.

• The isolated ions become wrapped in water molecules to form

hydrated ions.
The proper explanation

• The table below looks at how much energy is involved in each of these changes.
To be sure that you understand Atomisation energy

• This is the energy needed to produce 1 mole of isolated gaseous atoms starting
from an element in its standard state (gas for chlorine, and liquid for bromine, for
example - both of them as X2).

• For a gas like chlorine, this is simply half of the bond enthalpy (because breaking a
Cl-Cl bond produces 2 chlorine atoms, not 1). For a liquid like bromine or a solid
like iodine, it also includes the energy that is needed to convert them into gases.
• 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.

• In symbol terms:
• Hydration enthalpy (hydration energy)

• This is the energy released when 1 mole of gaseous ions dissolves in

water to produce hydrated ions.
 atomisation energy electron affinity hydration enthalpy overall
(kJ mol-1) (kJ mol-1) (kJ mol-1) (kJ mol-1)

F +79 -328 -506 -755

Cl +121 -349 -364 -592
Br +112 -324 -335 -547
I +107 -295 -293 -481
• Concentrating first on the final column which shows the overall heat
evolved when all the other processes happen. It is calculated by
adding the figures in the previous 3 columns.

• You can see that the amount of heat evolved falls quite dramatically
from the top to the bottom of the Group, with the biggest fall from
fluorine to chlorine.

• Fluorine produces a lot of heat when it forms its hydrated ion,

chlorine less so, and so on down the Group.
• Why is fluorine a much stronger oxidising agent than chlorine?

• What produces the very negative value for the enthalpy change when
fluorine turns into its hydrated ions? There are two main factors.

• The atomisation energy of fluorine is abnormally low. This reflects the

low bond enthalpy of fluorine.
• The main reason, though, is the very high hydration enthalpy of the fluoride ion. That is
because the ion is very small. There is a very strong attraction between the fluoride ions and
water molecules. The stronger the attraction, the more heat is evolved when the hydrated ions
are formed.

• Why the fall in oxidising ability from chlorine to bromine to iodine?

• The fall in atomisation energy between these three elements is fairly slight, and would tend to
make the overall change more negative as you go down the Group. The explanation doesn't lie
there!

• It is helpful to look at the changes in electron affinity and hydration enthalpy as you go down
the Group. Using the figures from the previous table:
 change in electron affinity change in hydration enthalpy
going from
(kJ mol-1) (kJ mol-1)
Cl to Br +25 +29
Br to I +29 +42
• You can see that both of these effects matter, but that the more
important one - the one that changes the most - is the change in the
hydration enthalpy.

• As you go down the Group, the ions become less attractive to water
molecules as they get bigger. Although the ease with which an atom
attracts an electron matters, it isn't actually as important as the
hydration enthalpy of the negative ion formed.

• The faulty explanation misses the mark even if you restrict it to

chlorine, bromine and iodine!
Using Electrode potential to explain relative
reactivity of halogens as oxidising agents
• As the electrode potential gets more positive the halogens on the left
become better oxidising agent . They accept electrons more readily
• As electrode potential values get less positive the halides on the right
become better reducing agents. They release electrons more readily
• Cl2 Accepts electrons more readily than I2 And I- ions release
electrons more readily than Cl- ions
• The reaction with the more negative electrode potential value goes
on the reverse direction