GROUP 7

Trends in Atomic Radius

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.

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 - F 2, 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.
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:

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.
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 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.

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 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 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.

Note: The reason for the red

solution is that iodine
dissolves in potassium
iodide (or other soluble
iodides) by reacting to give a
red ion, I3-. If the chlorine is
in excess, obviously there
isn't anything left for the
iodine to react with, and so it
remains as a dark grey
precipitate.

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.

Iodine won't oxidise any of the other halide ions (unless you
happened to have some extremely radioactive and amazingly rare
astatide ions - astatine is at the bottom of this Group).
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.
Unfortunately, this is often over-simplified to give what is actually a
faulty and misleading explanation. We'll deal with this first before
giving a proper explanation.
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.
In reality:
The halogen starts as diatomic molecules, X 2 - 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. (That's the stage of the
process we've been concentrating on in the faulty
explanation.)
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 the various terms:
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.

atomisati electr hydrati overa

on on on ll
energy affinit enthalp (kJ
(kJ mol-1) y y mol-1)
-
(kJ (kJ mol
mol-1) 1)
F +79 -328 -506 -755
Cl +121 -349 -364 -592
Br +112 -324 -335 -547
I +107 -295 -293 -481
There's quite a lot of data here to look at. Concentrate 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.

Note: Don't forget that we

are only talking about half of
a redox reaction in each
case. There will be other
energy terms involving
whatever the halogen is
oxidising. Those changes
will be overall endothermic.
For example, if chlorine
oxidises iodide ions to
iodine, that half of the total
reaction would need +481 kJ
mol-1, giving an enthalpy
change of reaction of (-592 +
 481) = -111 kJ per mole of I -
oxidised.

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 there is a fall in oxidizing 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.
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:
going from change in change in
electron hydration
affinity enthalpy
-1
(kJ mol ) (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.

Reactions with hydrogen

This shows the fall in reactivity of the halogens as you go down
Group 7.
Fluorine combines explosively with hydrogen even in the cold and
dark to give hydrogen fluoride gas.
Chlorine and hydrogen explode if exposed to sunlight or a flame to
give hydrogen chloride gas. Alternatively, you can make them
combine more peacefully if you light a jet of hydrogen and then
lower it into a gas jar of chlorine. The hydrogen continues to burn
and hydrogen chloride gas is again formed.
Bromine vapour and hydrogen combine with a mild explosion if
you put a flame in. Hydrogen bromide gas is formed.
Iodine and hydrogen only combine partially even on constant
heating. An equilibrium is set up between the hydrogen and the
iodine and hydrogen iodide gas.
All of these have an equation of the form:

. . . except the iodine case where you would have to replace the
arrow by a reversible sign.
Reactions with phosphorus
Warning! You have to be careful in comparing the rates of these
reactions because you won't necessarily be comparing like with
like. For example, it wouldn't be fair to compare the rate at which
phosphorus reacted with gaseous chlorine with the rate it reacted
with liquid bromine. There would be much more contact between
the particles with the phosphorus and the liquid bromine than
between phosphorus and chlorine gas.
The formation of trihalides, PX3
All of the halogens react with phosphorus to give, in the first
instance, phosphorus(III) halides - PX3.
There are two common forms of phosphorus which you might come
across in the lab - white phosphorus (sometimes called yellow
phosphorus) and red phosphorus. The white phosphorus is more
reactive than red phosphorus.

You can see that this is a violent reaction in the cold. You would
expect white phosphorus to behave even more dramatically.
When you write equations for these reactions, you have to be
careful how you write the phosphorus. White phosphorus is
molecular, consisting of P4 molecules. Red phosphorus is polymeric,
and you just use the symbol P.
So if you were writing the equation for the reaction between white
phosphorus and bromine, you would write:

. . . and for red phosphorus:

The formation of pentahalides, PX5

In an excess of chlorine or bromine, phosphorus reacts to form
phosphorus(V) chloride or bromide. Most simply, using white
phosphorus:
There is actually a reversible reaction involving phosphorus(III)
chloride and phosphorus(V) chloride.

An excess of chlorine obviously pushes this equilibrium to the

right.
Phosphorus and iodine don't seem to form a pentaiodide. The
probable reason is that you can't fit five large iodine atoms around
the central phosphorus atom.

Reactions with sodium

All of the halogens react with sodium to produce sodium halides.
You are probably familiar with the bright orange flame you get if
you lower hot sodium into a gas jar of chlorine gas, giving white
sodium chloride as the product.

Hot sodium will also burn in bromine or iodine vapour to produce

sodium bromide or sodium iodide. In each case, you would get an
orange flame and a white solid product.
I would imagine that sodium would burn in fluorine without
heating to give sodium fluoride, although I have never seen it done.

Reactions with iron

With the exception of iodine, iron burns in the halogen vapour to
give iron(III) halides. Iodine is less reactive, and only produces
iron(II) iodide.
Fluorine
Cold iron wool burns in cold fluorine to give iron(III) fluoride.
Anhydrous iron(III) fluoride is variously described as white or pale
green. Cotton and Wilkinson (a standard degree level inorganic
textbook) describes it as white.

This is a rapid reaction (the iron burns), and the iron has been
oxidised to an iron(III) compound - in other words, from an
oxidation state of zero in the iron metal to an oxidation state of +3
in the iron(III) compound.

Note: If you have forgotten

about oxidation states
(oxidation numbers), now is
the time to revise them.

Chlorine
If you pass chlorine gas over hot iron, the iron burns to form
iron(III) chloride. Iron(III) chloride forms black crystals if it is
anhydrous. Any trace of water present in the apparatus, or in the
chlorine, reacts with this to give reddish-brown colours.

The iron has been oxidised from an oxidation state of zero to +3.
Bromine
If you pass bromine vapour over hot iron, a similar but slightly less
vigorous reaction happens, this time producing iron(III) bromide.
Anhydrous iron(III) bromide is usually produced as a reddish-
brown solid.

Again the iron has been oxidised to an oxidation state of +3.

Iodine
The reaction between hot iron and iodine vapour only produces
iron(II) iodide, and is much less vigorous. The iron(II) iodide is said
to be grey. If you do this reaction, the product is always
contaminated with iodine, so it is difficult to be sure.

This time, the iodine is only capable of oxidising the iron as far as
the +2 oxidation state.
Reactions with solutions containing iron(II) ions
This time, we can only talk about the reactions of chlorine, bromine
and iodine. Wherever you have solutions, fluorine will react with
the water.
Chlorine and bromine are strong enough oxidising agents to oxidise
iron(II) ions to iron(III) ions. In the process, the chlorine is reduced
to chloride ions; the bromine to bromide ions.
It is easiest to see this with ionic equations:

For the bromine equation, just swap Cl for Br.

The very pale green solution containing the iron(II) ions will turn
into a yellow or orange solution containing iron(III) ions.
Iodine isn't a strong enough oxidising agent to oxidise iron(II) ions,
so there is no reaction. In fact the reverse reaction happens.
Iron(III) ions are strong enough oxidising agents to oxidise iodide
ions to iodine:

Reactions with sodium hydroxide solution

Once again, we will just look at this for chlorine, bromine and
iodine. We will start by looking at the chlorine case in detail
because it is common. The reaction of chlorine with cold sodium
hydroxide solution
The reaction between chlorine and cold dilute sodium hydroxide
solution is:

NaClO (sometimes written as NaOCl) is sodium chlorate(I). The

old name for this is sodium hypochlorite - and the solution on the
right-hand side of the equation is what is normally sold as bleach.
Now, think about this in terms of oxidation states.
Obviously the chlorine has changed oxidation state because it has
ended up in compounds starting from the original element.
Checking all the oxidation states shows:

The chlorine is the only thing to have changed oxidation state. Has
it been oxidised or reduced? Yes! Both! One atom has been reduced
because its oxidation state has fallen. The other has been oxidised.
This is a good example of a disproportionation reaction. A
disproportionation reaction is one in which a single substance is
both oxidised and reduced.
The reaction of chlorine with hot sodium hydroxide solution
The reaction between chlorine and hot concentrated sodium
hydroxide solution is:

The unfamiliar product this time is sodium chlorate(V) - NaClO 3.

As before, check the oxidation states of everything in the equation.
Once again, you will find that the only thing to have changed is the
chlorine. It goes from 0 in the chlorine molecules on the left-hand
side to -1 (in the NaCl) and +5 (in the NaClO3).
This is also a disproportionation reaction.
Building equations for these reactions
Actually, the first one is simple, and most people would just write it
down. The second one is more difficult, and one way of building it
up is using oxidation states.
You would need to have learnt the two main products of the
reaction. So write those down:

Now think about the oxidation state changes. To go to NaCl, the

oxidation state of the chlorine has fallen from 0 to -1.
To go to NaClO3, it has increased from 0 to +5.
The positive and negative oxidation state changes must cancel out,
so for every NaClO3 formed, there must be 5 NaCl. Write that
down:
Now it is a simple job to balance the sodiums and the chlorines.
When you have finished, you will find that you have enough
hydrogens and oxygens left over to make 3H 2O. That seems
reasonable!
The reactions involving bromine and iodine
These are essentially similar to the chlorine, the difference being
the temperatures at which things happen. The tendency to form the
ion with the halogen in the +5 oxidation state increases rapidly as
you go down the Group.
Bromine and sodium hydroxide solution
With bromine, the formation of the sodium bromate(V) happens at
a much lower temperature, down to room temperature. If you want
to make a solution of sodium bromate(I), you have to do the
reaction at about 0C.
Iodine and sodium hydroxide solution
THE REDOX REACTIONS BETWEEN HALIDE IONS AND
CONCENTRATED SULPHURIC ACID
This page describes and explains the redox reactions involving
halide ions and concentrated sulphuric acid. It uses these reactions
to discuss the trend in reducing ability of the ions as you go from
fluoride to chloride to bromide to iodide.
The Facts
There are two different types of reaction which might go on when
concentrated sulphuric acid is added to a solid ionic halide like
sodium fluoride, chloride, bromide or iodide. The concentrated
sulphuric acid can act both as an acid and as an oxidising agent.
Concentrated sulphuric acid acting as an acid
The concentrated sulphuric acid gives a hydrogen ion to the halide
ion to produce a hydrogen halide. Because this is a gas, it
immediately escapes from the system. If the hydrogen halide is
exposed to moist air, you see it as steamy fumes.
As an example, concentrated sulphuric acid reacts with solid
sodium chloride in the cold to produce hydrogen chloride and
sodium hydrogensulphate.

All of the halide ions (fluoride, chloride, bromide and iodide)

behave similarly.

Concentrated sulphuric acid acting as an oxidising agent

With fluoride or chloride ions
Concentrated sulphuric acid isn't a strong enough oxidising agent
to oxidise fluoride or chloride ions. In those cases, all you get
produced are the steamy fumes of the hydrogen halide - hydrogen
fluoride or hydrogen chloride.
You can look at this another way - from the point of view of the
halide ions. The fluoride and chloride ions aren't strong enough
reducing agents to reduce the sulphuric acid.
Whichever way you look at it, all you get is the hydrogen halide!
That isn't true, though, with bromides and iodides.
With bromide ions
The bromide ions are strong enough reducing agents to reduce the
concentrated sulphuric acid. In the process the bromide ions are
oxidised to bromine.

The bromide ions reduce the sulphuric acid to sulphur dioxide gas.
This is a decrease of oxidation state of the sulphur from +6 in the
sulphuric acid to +4 in the sulphur dioxide.

You can combine these two half-equations to give the overall ionic
equation for the reaction:

What you see in this reaction are the steamy fumes of hydrogen
bromide contaminated with the brown colour of bromine vapour.
The sulphur dioxide is a colourless gas, so you couldn't observe its
presence directly.
With iodide ions
Iodide ions are stronger reducing agents than bromide ions are.
They are oxidised to iodine by the concentrated sulphuric acid.

The reduction of the sulphuric acid is more complicated than

before. The iodide ions are powerful enough reducing agents to
reduce it
first to sulphur dioxide (sulphur oxidation state = +4)
then to sulphur itself (oxidation state = 0)
and all the way to hydrogen sulphide (sulphur oxidation
state = -2).
The most important of this mixture of reduction products is
probably the hydrogen sulphide. The half-equation for its
formation is:

Combining these last two half-equations gives:

Important! Don't try to

remember this equation - the
chances of you ever needing
it in an exam are tiny. Learn
 how to work out electron-
half-equations and combine
them to make the overall
equation. A bit of time
acquiring that skill will save
you a lot of pointless
learning.

This time what you see is a trace of misty(white) fumes of hydrogen

iodide, but mainly lots of iodine. The reaction is exothermic and so
purple iodine vapour is formed, and probably dark grey solid
iodine condensing around the top of the tube. There will also be red
colours where the iodine comes into contact with the solid iodide.
The red colour is due to the I 3- ion formed by reaction between I 2
molecules and I- ions.
You won't see the colourless hydrogen sulphide gas, but might pick
up its "bad egg" smell if you were foolish enough to smell the
intensely poisonous gases evolved!

Summary of the trend in reducing ability

Fluoride and chloride ions won't reduce concentrated
sulphuric acid.
Bromide ions reduce the sulphuric acid to sulphur dioxide.
In the process, the bromide ions are oxidised to bromine.
Iodide ions reduce the sulphuric acid to a mixture of
products including hydrogen sulphide. The iodide ions are
oxidised to iodine.
Reducing ability of the halide ions increases as you go down
the Group.
Explaining the trend( again lol :) )
if you ignore fluoride ions. The argument goes like this:
When a halide ion acts as a reducing agent, it gives electrons to
something else. That means that the halide ion itself has to lose
electrons.
The bigger the halide ion, the further the outer electrons are from
the nucleus, and the more they are screened from it by inner
electrons. It therefore gets easier for the halide ions to lose electrons
as you go down the Group because there is less attraction between
the outer electrons and the nucleus.
It sounds convincing, but it only tells part of the story. We need to
look in some detail at the energetics of the change.

A more detailed explanation (for the boring people)

Looking at how the enthalpy changes vary from halogen to halogen
We need to compare the amount of heat evolved or absorbed when
you convert a solid halide (like sodium chloride) into molecules of
the halogen.
Taking sodium chloride as an example:
We need to supply the energy to break the attractions
between the ions in the sodium chloride. In other words, we
need to supply the lattice enthalpy.
We need to supply the energy to remove the electron from
the chloride ion. This is the reverse of the electron affinity
of the chlorine. You can get this figure by looking up the
electron affinity in a Data Book and giving it a positive
rather than a negative sign.
We then recover some energy when the chlorine atoms turn
into chlorine molecules. Energy is released when the bonds
are formed.
Chlorine is simple because it is a gas. With bromine and
iodine, heat will also be released when they condense to a
liquid or solid. To take account of this, it is better to think
of this in terms of atomisation energy rather than bond
energy. The number we want is the reverse of atomisation
energy.
Atomisation energy 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).
Look carefully at the diagram so that you see how this all fits
together:

Note: The term "lattice

 enthalpy" used here should
more accurately be described
as "lattice dissociation
enthalpy".

What we need to do is calculate the enthalpy change shown by the

green arrow in the diagram for each of the halogens so that we can
make a comparison. The diagram shows that the overall change
involving the halide ions is endothermic - the green arrow is pointing
upwards towards a higher energy.
This isn't the total enthalpy change for the whole reaction. Heat will be
given out when the changes involving the sulphuric acid occur. That
will be the same irrespective of which halogen you are talking about.
The total enthalpy change will be the sum of the enthalpy changes for
the halide ion half-reaction and the sulphuric acid half-reaction.
The table shows the energy changes which vary from halogen to
halogen. We are assuming that you start from solid sodium halide. The
values for the lattice enthalpies for other solid halides would be
different, but the pattern will still be the same.
heat heat heat sum of
neede needed released these
d to to in (kJ
break remove forming mol-1)
up electro halogen
NaX n from molecule
lattice halide s
(kJ ion (kJ mol-
-1 1
mol ) (kJ )
mol-1)
F +902 +328 -79 +1151
Cl +771 +349 -121 +999
Br +733 +324 -112 +945
I +684 +295 -107 +872

The overall enthalpy change for the halide half-reaction:

Look at the final column of figures.
Notice that the sum of these enthalpy changes gets less endothermic
as you go down the Group. That means that the total change
(including the sulphuric acid) will become easier as you go down
the Group.
The amount of heat given out by the half-reaction involving the
sulphuric acid must be great enough to make the reactions with the
bromide or iodide feasible, but not enough to compensate for the
more positive values produced by the fluoride and chloride half-
reactions.
I don't know what the real value for the sulphuric acid half-
reaction to produce sulphur dioxide is, but it must be something
like -980 kJ mol-1. Try the effect of combining that value with the
overall values in the table to see what happens to the total enthalpy
change of reaction for each halogen.

Exploring the changes in the various energy terms

Which individual energy terms in the table are most important in
making the halogen half-reaction less endothermic as you go down
the Group?
Chlorine to iodine
Considering the halogens from chlorine to iodine, it is the lattice
enthalpy which has fallen most. It falls by 87 kJ mol -1. By contrast,
the heat needed to remove the electron has only fallen by 54 kJ mol -
1
.
Both of these terms matter, but the fall in lattice enthalpy is the
more important. This falls because the ions are getting bigger. That
means that they aren't as close to each other, and so the attractions
between positive and negative ions in the solid lattice get less.
The simplified explanation that we mentioned earlier concentrates
on the less important fall in the amount of energy needed to remove
the electron from the ion. That's misleading!
Fluorine

Fluoride ions are very difficult to oxidise to fluorine. The table

shows that this isn't anything to do with the amount of energy
needed to remove an electron from a fluoride ion. It is actually
easier to remove an electron from a fluoride ion than from a
chloride ion.

In this case, to make the generalisation that an electron gets easier

to remove as the ion gets bigger is just plain wrong!

Fluoride ions are so small that the electrons feel an abnormal

amount of repulsion from each other. This outweighs the effect of
their closeness to the nucleus and makes them easier to remove
than you might expect.

There are two important reasons why fluoride ions are so difficult
to oxidise.
The first is the comparatively very high lattice enthalpy of the solid
fluoride. This is due to the small size of the fluoride ion, which
means that the positive and negative ions are very close together
and so strongly attracted to each other.
The other factor is the small amount of heat which is released when
the fluorine atoms combine to make fluorine molecules. (Scroll
back and look at the table again.)
This is because of the low bond enthalpy of the F-F bond. The
reason for this low bond enthalpy is discusssed on a separate page.

What if the halide ions were in solution rather than in a solid?

We have concentrated on the energetics of the process starting
from solid halide ions because that's what you use if you try to
oxidise them using concentrated sulphuric acid. What about
oxidising them in solution using some different oxidising agent?

The trend is exactly the same. Fluoride ions are difficult to oxidise
and it gets easier as you go down the Group towards iodide ions.
Looked at another way, fluoride ions aren't good reducing agents,
but iodide ions are.

The explanation this time has to start from the hydrated ions in
solution rather than solid ions. In a sense, this has already been
done on another page.
Fluorine is a very powerful oxidising agent because it very readily
forms its negative ion in solution. That means that it will be
energetically difficult to reverse the process.

By contrast, for the energetic reasons you will find discussed, iodine
is relatively reluctant to form its negative ion in solution. That
means that it will be relatively easy to persuade it to revert to
iodine molecules again.