Trends in Group 7

Characteristic physical properties

Explain, in terms of van der Waals forces, the trend in the boiling points of
Cl2, Br2 and I2;
As you move down group 7, the boiling point increases.

1. The number of electrons increases, leading to an increase in Van der Waals

forces between molecules.

2. Therefore more energy is needed to break the bonds, so hence a higher

boiling point.

Redox reactions and trends in reactivity of Group 7 elements and their

compounds
Describe the redox reactions, including ionic equations, of the Group 7
elements Cl2, Br2 and I2 with other halide ions, in the presence of an organic
solvent, to illustrate the relative reactivity of Group 7 elements;
Halogens form solutions of different colours.
Halogen
Cl2
Br2
I2
Violet

Pale

Water
green
Orange

Pale

Cyclohexane
green
Orange
Brown

Any colour change with show whether a redox reaction has taken place. The mixture
is usually shaken with an organic solvent, Cyclohexane, to distinguish between
bromine and iodine.
Chlorine oxidises both Bromide ions and Iodide ions:
Cl2(aq) + 2Br- (aq) ----> 2Cl-(aq) + Br2(aq) - Orange in water and in Cyclohexane
Cl2(aq) + 2I-(aq) ----> 2Cl-(aq) + I2(aq) - Brown in water and purple in Cyclohexane

Bromine oxidises Iodide ions only:

Br2(aq) + 2I-(aq) ----> 2Br-(aq) + I2(aq) - Brown in water and purple in Cyclohexane
Explain the trend in reactivity of Group 7 elements down the group from the
decreasing ease of forming negative ions, in terms of atomic size, shielding
and nuclear attraction;
As you go down group 7, they become less reactive.

1. Atomic radius increases

2. Electron shielding increases

3. The nuclear attraction between the electrons and the nucleus therefore
increases, making it harder for the outer shell to gain an electron into the psubshell.

Describe the term disproportionation as a illustrated by:

(i) the reaction of chlorine with water as used in water purification,
Cl2(aq) + H2O(l) -----> HClO(aq) + HCl(aq)
(ii) the reaction of chlorine with cold, dilute aqueous sodium hydroxide, as used to
form bleach,
Cl2(aq) + 2NaOH(aq) ----> NaCl(aq) + NaClO(aq) + H2O(l)
The above two equations are both example of disproportionation reactions as the
chlorine is both oxidised and reduced in both.
Interpret and make predictions from the chemical and physical properties of
the Group 7 elements and their compounds;
Group 7 all share the same characteristics
Covalent diatomic molecules (I2,F2 etc)
Structure Simple molecular
Held together by van der Waals forces between molecules.
Redox Character Oxidising agents.

Halogen + electron ----> Halide ion

Reactivity decreases down the group.
Some Halides compounds are used in products as most are very stable.

1. NaCl is common salt

2. NaF and SnF2 are fluoride compounds added to toothpaste to prevent

tooth decay.

3. CaF2 or fluorite is used to makes lenses to focus infrared light.

Contrast the benefits of chlorine use in water treatment

(killing bacteria) with associated risks (hazards of toxic chlorine gas and possible
risks from formation of chlorinated hydrocarbons);
Chlorine makes water safer to drink by sterilising it through killing bacteria.
However, chlorine reacts with organic matter to from chlorinated hydrocarbons,
which may cause cancer. Chlorine is also toxic.

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Characteristic reactions of halide ions
Describe the precipitation reactions, including ionic equations, of the aqueous
anions Cl, Br and I with aqueous silver ions, followed by aqueous ammonia;

1. An unknown halide is dissolved in water.

2. Aqueous silver nitrate (AgNO3) is added.

3. The Ag+ ions react with the halide ions to form coloured precipitates.

4. If unsure about the colour, adding aqueous ammonia (NH3) may help
distinguish as different precipitates have different solubility in the ammonia.

Chloride
Ag+(aq) + Cl-(aq) -----> AgCl(s) - White precipitate, soluble in dilute NH3

Bromide
Ag+(aq) + Br-(aq) -----> AgBr(s) - Cream precipitate, soluble in concentrated NH3
Iodide
Ag+(aq) + I-(aq) -----> AgI(s) - Yellow precipitate, insoluble in concentrated NH3
These types of reactions are called precipitation reactions. They take place in
aqueous solutions when aqueous ions react together to form a solid precipitate.
Fluoride ions produces no precipitate with silver nitrate.

Trends in Atomic Radius

You can see that the atomic radius increases as you go down the Group.

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 the electron configurations of fluorine and chlorine:

F: 1s22s22p5
Cl: 1s22s22p53s23p5
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 screening of the inner electrons.

This is equally true for all the other atoms in Group 17. The outer electrons always
feel a net pull of 7+ from the center. 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.

As shown in the figure above, electronegativity decreases from fluorine to

iodine; the atoms become less effective at attracting bonding pairs of electrons as
they grow larger. This can be visualized using dots-and-crosses diagrams for
hydrogen fluoride and hydrogen chloride.

The bonding electrons between the hydrogen and the halogen experience the same
net charge of +7 from either the fluorine or the chlorine. However, in the chlorine
case, the nucleus is further away from the bonding pair. Therefore, electrons are not
as strongly attracted to the chlorine nucleus as they are to the fluorine nucleus.
The stronger attraction to the closer fluorine nucleus makes fluorine is more
electronegative.

Summarizing the trend down the group

As the halogen atoms get larger, any bonding pair is farther and farther away from
the halogen nucleus, and so is less strongly attracted towards it. Hence, the
elements become less electronegative as you go down the Group,.

Trends in First Electron Affi nity

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 other words, it is
the energy released (per mole of X) when the following reaction takes place:
X(g)+eX(g)
First electron affinities have negative values. For example, the first electron affinity
of chlorine is -349 kJ mol -1. By convention, a negative sign indicates a release of
energy.

The trend down the group is not consistent; the graph above shows a tendency is
for the electron affinities to become more positive (less energy is given off),
but fluorine does not follow this pattern. 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 larger atom, the attraction from the more positive nucleus is offset by the
additional screening electrons, so each incoming electron again experiences the
effect of a net 7+ charges from each center. An incoming electron is farther from
the nucleus of the larger atom, and therefore feels a smaller attraction. The electron
affinity therefore decreases down the group.
Fluorine is a very small atom, and an incoming electron is close to the nucleus.
However, the new electron enters a region of space already very negatively charged
because of the existing electrons. Because the fluorine atom is small, the existing
electron density is very high, offsetting some of the attraction from the nucleus.
This effect is enough to lower the electron affinity below that of chlorine.

Trends in Melting Point and Boiling Point

The figure below shows that the melting and boiling points of the halogens increase
down the group. The graph clearly shows that at room temperature, fluorine and
chlorine are gases, bromine is a liquid, and iodine is a solid.

All halogens exist as diatomic molecules: F2, Cl2, etc. The intermolecular attractions
between one molecule and its neighbors are van der Waals dispersion forces. As the
molecules get larger there are more electrons to move around and form the
temporary dipoles that 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.

Solubility
Because fluorine reacts violently with water to produce hydrogen fluoride gas (or
hydrofluoric acid, in solution) and a mixture of oxygen and ozone, analyzing its
solubility is fruitless. Chlorine, bromine and iodine are soluble in water, but there is
no pattern in their solubilities. 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 dissolved in water is pale green. Bromine solution is yellow or dark orangered depending the concentration. Iodine in water is pale brown. Chlorine reacts with
water to some extent, giving a mixture of hydrochloric acid and chloric(I) acid (also
known as hypochlorous acid). The reaction is reversible, and at any time only a third
of the chlorine molecules participate in the reaction, shown below:
Cl2+H2OHCl+HClO
Chloric(I) acid is sometimes denoted HOCl; this format better represents the actual
arrangement of the atoms. Bromine and iodine react with water in a similar way,
but to a much lesser extent. In both cases, about 99.5% of the halogen remains
unreacted.

The solubility of iodine in potassium iodide solution

Although iodine is only slightly soluble in water, it dissolves readily in potassium
iodide solution; the resulting solution is dark red-brown. A reversible reaction
between iodine molecules and iodide ions produces I3 ions; these ions are
responsible for the color. In the laboratory, iodine is often produced by oxidation of a
solution containing iodide ions; this reaction should be familiar to many
undergraduate students. As long as there are excess iodide ions present, the
iodine reacts to form I3. Once the iodide ions have all reacted, iodine is
precipitated as a dark grey solidthere is no reactant to keep it in solution.

Solubility in hexane
As nonpolar molecules, the halogens are much more soluble in organic solvents
such as hexane than they are in water. Hexane and the halogens are all non-polar
molecules whose dominant intermolecular attractions are van der Waals dispersion
forces. The attractions broken (between hexane molecules and between halogen
molecules) are similar in magnitude to the new attractions formed when the two
substances mix.

Bond enthalpies (bond energies or bond strengths)

Bond enthalpy is the heat required 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. For chlorine, Cl 2(g), it is the heat energy required to carry out
this change per mole:

Below is the same reaction with bromine:

Bond enthalpy in the halogens, X 2 (g)

A covalent bond occurs because the bonding electron 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 depends, among other things, on the distances from the
bonding pair to each of the two nuclei.

As mentioned before, the bonding pair feels a net attraction of 7+ from both ends
of the bond. As the atoms get larger down the group, the bonding pair is
progressively farther from the nuclei; it is reasonable to expect the bond strength to
decrease. The figure below shows the actual bond enthalpies of the diatomic
halogens:

The bond enthalpies of the Cl-Cl, Br-Br and I-I bonds decrease as predicted, but the
F-F bond enthalpy deviates significantly. Because fluorine atoms are so small, a
strong bond is expected; in fact, it is remarkably weak. In addition to the
bonding electrons between the two atoms, each atom has 3 non-bonding pairs of
electrons in the outer levellone pairs. If the bond length is very short (as is the
case with F-F), the lone pairs on the two atoms close enough together to cause a
significant amount of repulsion.

In the case of fluorine, this repulsion is great enough to counteract much of the
attraction between the bonding pair and the two nuclei; this weakens the bond.

Bond enthalpies in the hydrogen halides, HX(g)

If a halogen atom is attached to a hydrogen atom, this effect is not observed; there
are no lone pairs on a hydrogen atom. Bond enthalpies for H-X bonds are given in
the figure below:

With larger atoms, the bonding pair is increasingly distant from the nucleus. The
attraction is lessened, and the bond weakenedthis is perfectly consistent with the
data, with no complications.
This is an important factor in the thermal stability of the hydrogen halides because
it indicates how easily they are broken into hydrogen and the halogen on heating.
Hydrogen fluoride and hydrogen chloride are thermally stablethey do not split into
hydrogen and fluorine or chlorine if heated to normal laboratory temperatures.
Hydrogen bromide breaks down slightly into hydrogen and bromine on heating, and
hydrogen iodide reacts to an even greater extent. Weaker bonds are more easily
broken.
Breaking the hydrogen-halogen bond is only one of the steps in the overall reaction,
of coursethe end products are not hydrogen atoms and halogen atoms, but the
diatomic molecules H2 and X2. It is a useful exercise to use bond enthalpies and
atomization 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 atomization enthalpies for the halogens avoids this
problem.