Group VII

Group VII
The elements in group VII are known as ……………………………...
F
All have the electronic configuration…..ns2 np5.
Cl
They are all …………………………… and exist has separate ………………………………. molecules.
Br
I
At

Properties of halogens
Fluorine Chlorine Bromine Iodine
Physical state and colour(at rtp)

Melting point -220 -101 -72 114

Atomic radius (nm) 0.064 0.099 0.111 0.128
Ionic radius (mn) 0.136 0.181 0.195 0.216
Electronegativity 4.0 3.0 2.8 2.5
1stIonisation energy 1680 1260 1140 1010
1st Electron affinity -348 -364 -342 -314

Changes in the Halogens’ physical properties

The halogens exist as …………………… molecules that interact through ………………………………………forces,

which ………………………..…… in strength as the atoms become ……………………………….; thus F2 is a yellow gas,
Cl2 a yellow-green gas, Br2 is a brown orange liquid and I2 a purple-black solid.

Trends in melting and boiling temperatures

Atomic and ionic radius

Electronegativity
The first ionization energy

Electron affinity

Bond enthalpy

It is the energy required to break one mole of a covalent bond to produce individual atoms in the gaseous
state.
F-F(g)  2 F(g)
Group VII
Group VII
The elements in group VII are known as halogens.
F
The term ‘halogen’ is derived from Greek meaning ‘salt producing’. Halogens are very reactive
Cl
and readily form salts.
Br
All have the electronic configuration…..ns2 np5.
I
They are all non-metals and exist has separate diatomic molecules.
At

Properties of halogens
Fluorine Chlorine Bromine Iodine
Physical state and colour(at rtp) Pale yellow gas Green gas Red brown liquid Shiny greyish solid
Melting point -220 -101 -72 114
Atomic radius (nm) 0.064 0.099 0.111 0.128
Ionic radius (mn) 0.136 0.181 0.195 0.216
Electronegativity 4.0 3.0 2.8 2.5
1stIonisation energy 1680 1260 1140 1010
1st Electron affinity -348 -364 -342 -314

Regular changes in the Halogens’ Physical properties

The halogens exist as diatomic molecules that interact through dispersion forces, which increase in
strength as the atoms become larger; thus F2 is a yellow gas, Cl2 a yellow-green gas, Br2 is a brown orange
liquid and I2 a purple-black solid.

Melting and boiling temperatures increases down the group because as the size of halogen increases as
the number of electrons increase. This increases the strength of London forces. Therefore more energy is
required to overcome the forces of attraction between molecules.

Down the group, atomic and ionic radius increases because the number of shells increases. Ionic radius
is larger than the atomic radius, because, the effective nuclear charge decreases with the addition of an
extra electron to the outer shell. Repulsion exists between the electrons and the added electrons.

Electronegativity decreases down the group. As the number of shells increases, the shielding of the
nucleus by inner shell electrons increases and the size of the atom increases so the ability of the nucleus
to attract electron pair is reduced.

The first ionization energy decreases down the group as shielding of the nucleus effect increases.
 Electron affinity generally decreases down the group (from chlorine to iodine). This is because as the size
of the atom increases, the attraction between the incoming electron and
the nucleus decreases.
The first electron affinity of fluorine is smaller than that of
chlorine because in fluorine the electron has to be added to an
atom of small volume. Fluorine atom is very small so the electron
density is very high. There is an extra repulsion between the
incoming electrons and the outer electrons of fluorine, which
decreases the attraction from the nucleus.

Bond enthalpy

It is the energy required to break one mole of a covalent bond to produce individual atoms in the gaseous
state.
F-F(g)  2 F(g)

A covalent bond works because the bonding pair is attracted to both the nuclei at
either side of it. So, the force of attraction between the individual atoms in a molecule
depends on the distance from the bonding pairs to the two nuclei. Therefore, short
bonds are stronger than long bonds. As the atoms get bigger the bonding pair gets
further from the nuclei and so the strength of the bond decreases.

Bond enthalpies decreases down

the group from fluorine to
iodine, however fluorine has
much lower bond enthalpy than
expected.
Bonding in F-F is very short and
each atom has three non-
bonding pairs of electrons in the
outer shell. Therefore when the
non-bonding pairs of electrons in
the outer shell is brought so
together, they repel and
weakens the bond.
Chemical properties

Why are halogens so reactive?

The group VII elements react with most metals and non-metals to form ionic and covalent compounds.
These non-atoms must gain one electron to fill its outer shell. It accomplishes this filling in either two
ways:
1. Gaining an electron from a metal atom thus forming a negative ion as metals forms a positive ion.
2. Sharing electron pair with non-metal atom, thus forming a covalent bond.

Reactions of halogens

The reactivity of halogens decreases down the group.

Down the group, reactivity reflects the decrease in electronegativity: F2 is the most reactive
and I2 the least reactive. The exceptional reactivity of elemental F2 is also related to the
weakness of the F-F bond. Since F is small, the bond is short, but the lone pairs on each F atom
repel those on the other, which weakens the bond. As a result of these factors, F2 reacts with
every element (except He, and Ar) in many cases explosively.

The halogens display the largest range in electronegativity of any group but all are
electronegative enough to behave as non-metals.

Electron affinity also decreases down the group, therefore is it less easier to form anions.

Oxidation Power

 Halogens are strong oxidizing agent (as they need an electron to complete their outer shell), as
they accept electrons and get reduced.
 They can remove electron from other substances.
 The oxidizing power of the halogen decreases as we move down the group from F to I.
F2 > Cl2 > Br2 > I2

F2(g) + 2e  2F-(aq)

Cl2(g) + 2e  2Cl-(aq)

Br2(l) + 2e 2Br-(aq)

I2(aq) + 2e  2I-(aq)
Displacement reaction
Reaction with solutions of other halides

A halogen will displace a less reactive halogen from its salts.

Since F2 is the strongest oxidizing agent, it will oxidize all other halide ions to halogens.
F2 + 2 X–  2 F– + X2 (X = Cl, Br, I)

Similarly, Cl2 will displace Br– and I– ions from their solutions while Br2 will displace I– ions only.

Cl2 + 2X–  2Cl– + X2 (X = Br, I)

Br2 + 2I–  2Br– + I2

Example:

Cl2(g) + 2Br-(aq)  2Cl-(aq) + Br2(aq)

Orange colour will appear in solution on adding chlorine

Cl2(aq) + 2I-(aq)  2Cl-(aq) + I2(aq)

Brown colour will appear in solution on adding chlorine

Br2(aq) + 2I-(aq)  2Br-(aq) + I2(aq)

Brown colour will appear in solution after adding bromine

I2(aq) + 2Cl-(aq)  no reaction

I2(aq) + 2Br-(aq)  no reaction

Br2(aq) + 2Cl-(aq)  no reaction

As size increases down a group, the ability of the atoms to accept electrons decreases and hence their
oxidising power decreases.

The displacement of bromine by chlorine is used in the extraction of bromine from sea water.

Cl2 + Br-  Br2 + 2Cl-

Halogens higher in the group can oxidise halide ions lower down.
Chlorine will displace bromide and iodide ions from solution.
Bromine will displace iodide ions from solution, but not chloride ions.
Iodine cannot displace either bromide or chloride ions from solution.

The redox behavior of the halogens is based on properties such as electron affinity, ionic charge density
and electronegativity.
Reaction of halogens with non-metals

- Halogens react with non-metals to achieve noble gas configuration through covalent bonding.
- Fluorine is the most electronegative element, so its oxidation number is always -1. It means
fluorine forms only one covalent bond.
- Other halogens can have -1, +1, +3, +5 and +7, meaning they can form more than one covalent
bonds.

Fluorine reacts directly with all non-metals except nitrogen, helium, neon and argon.

C + 2 F2  CF4
Xe + 2 F2  XeF4

Chlorine and bromine are much less reactive than fluorine. They will not react directly with any of the
noble gases, carbon, nitrogen or oxygen.

Iodine does not combine with these elements nor with sulphur, but it reacts readily with phosphorous.

Reaction with phosphorous

In a limited supply of chlorine, PCl3 is formed, which then reacts with more chlorine to form PCl5.
2P + 3 Cl2  2 PCl3
2 PCl3 + Cl2  PCl5

In excess chlorine PCl5 is formed, 2P + 5 Cl2  2 PCl5

Iodine reacts with the red allotrope of phosphorus to form PI3.

2P + 3 l2  2 Pl3

Reaction with metals

Metals react with halogens on heating to form halides in which halogen is in the -1 oxidation state.

2Na(s) + Cl2(g)  NaCl(s)

Mg(s) + Cl2(g)  MgCl2(s)

Iron reacts with chlorine and bromine to form iron(III)halides.

Chlorine oxidizes iron to iron(III)chloride

2 Fe(s) + 3Cl2(g)  2 FeCl3(s)
However, Iron reacts iodine to form iron(II)iodide.
 Fe(s) + I2(s)  FeI2

The disproportionation reactions of halogens with alkali

Disproportionation reaction is a reaction in which one particular reactant is simultaneously

oxidized and reduced.
Chlorine, bromine and iodine react with aqueous sodium hydroxide to form different products
depending on conditions.

Reaction with alkali

With alkali at room temperature

Chlorine, Bromine and iodine all react with aqueous NaOH by disproportionation reaction to
produce a mixture of halide salts, halate(I) salts and water.

Chlorine is both oxidised and reduced when it reacts with sodium hydroxide solution

With hot alkali

This is also a disproportionation reaction; the halogen is oxidized to the +5 state rather than +1
state as in the case of cold alkali.
They react with hot alkali to form halide salts, halate(V)salts (Sodium chlorate) and water.

3Cl2(aq) + 6NaOH(aq)  5NaCl(aq) + NaClO3(aq) + 3H2O(l)

Bromine and iodine reacts similarly.

Reaction with reducing agents

 Chlorine and bromine oxidizes iron(II) ion to iron(III) ion.

Cl2(aq) + 2Fe2+(aq)  2 Cl-(aq) + 2Fe3+(aq)

Iodine is too weak to oxidize iron(II) ion to iron(III) ion. The reverse happens. Iodide ions are
oxidized by Fe3+ ions to iodine.

2I-(aq) + 2Fe3+(aq)  I2(aq) + 2Fe2+(aq)

Test for halogens

Test Chlorine Bromine Iodine

With moist red litmus Bleach rapidly Bleach more slowly than No effect
Cl2
With moist blue litmus Turns red and then Turns red and then bleach No effect
bleach (slowly than Cl2)
With starch solution No effect No effect Turns blue black
Add KBr followed by Brown solution. On
hexane and shake shaking hexane layer No effect No effect
vigorously turns brown

Hydrogen halides

The halogens form colourless gaseous hydrogen halides (HX) through direct combination with H2 or
through the action of a concentrated acid on the metal halide (a non-oxidising acid is used for HBr and
HI).

Fluorine reacts explosively with hydrogen under all conditions.

H2(g) + Cl2(g)  2HCl(g) explodes in direct sunlight, proceeds slowly in dark

H2(g) + Br2(g)  2HBr(g) at 300oC in the presence of platinum catalyst
H2(g) + I2(g) ↔ 2HCl(g) at 300oC in the presence of platinum catalyst, proceeds
slowly and only partially

CaF2(s) + H2SO4(l)  CaSO4(s) + 2HF(g)

3 NaBr(s) + H3PO4(l)  Na3PO4(s) + 3HBr(g)

In water, gaseous (hydrogen halides) HX molecules form a hydrohalic acid. Only HF, with its relatively
short, strong bond forms a weak acid. The ions are hydrated.
HF(g) + H2O(l) ↔ H3O+(aq) + F-(aq)
The others completely dissociate

HBr(g) + H2O(l)  H3O+(aq) + Br-(aq)

The extent to which dissociation occurs is largely depends on the HX bond strength.

weakest acid strongest acid

The HX bond strength decreases in the order HCl, HBr and HI. Hence acidity increases in the order HCl,
HBr and HI with HI being the most acidic.

HF has an anomalous boiling temperature because it forms strong intermolecular hydrogen bonds.

HF is exceptional: it is the weakest acid because in addition to the greatest strength of the H-F bond, it
also forms hydrogen bonds.

Solubility and colour of solutions

Halogens, being non polar in nature do not readily dissolve in a polar solvent like water, however, fluorine
is such a powerful oxidizing agent that it reacts with water vigorously even at low temperature
(exothermally), oxidizing the oxygen to produce O2, some O3 and HFO (Hypofluorous acid).

Chlorine and bromine are fairly soluble. This is because they react reversibly with water to form a
mixture of acids (hydrochloric acid, HCl and hypochlorous acid, HOCl)

Cl2 + H2O HClO + HCl

Chlorine reacts with water forming a solution that is called chlorine water (aqueous chlorine) which is
pale green in colour.

HClO is chloric (I) acid. It is a mild oxidising agent and effective at killing bacteria without being harmful
to humans. For this reason a small amount of chlorine dissolved in water will sterilise the water and
chlorine is widely used in swimming pools and in water treatment for this reason.

Chlorine is toxic to humans in anything other than very small doses, so care must be taken not to over-
chlorinate the water supply.
Aqueous solution of bromine is called bromine water which is brown red. Bromine dissolves and reacts
with water in a similar way, but to a lesser extent.

Iodine is almost insoluble in water but soluble in potassium iodide solution because of the formation of
I3- ions (triiodide, I3–).The solution is pale brown.
KI + I2 KI3

All halogens are more soluble in inert organic solvent such as CCl4 or hexane than in water.

Cl2 Br2 I2
Colour green red-brown shiny grayish black
In water pale green red-brown pale brown
In hydrocarbon solvent pale green red-brown violet

Halide salts
 Group I and II metals form ionic salts of formula MX and MX2respectively.

Test for halide ions in solution

The analysis of the halide ions is based on the solubilities of the silver halides

Test Chloride Bromide Iodide

Add dilute nitric acid, then
silver nitrate solution
To distinguish the
precipitate, add dilute
ammonia and
concentrated ammonia
solution
White precipitate Cream precipitate of Yellow precipitate of
of AgCl(s) AgBr(s) AgI(s)
Precipitate Precipitate slightly Precipitate insoluble in
soluble in both soluble in dilute both
ammonia and soluble in
concentrated ammonia

Ag+(aq) + Cl- (aq)  AgCl(s) white precipitate

Ag+(aq) + Br- (aq)  AgBr(s) cream precipitate
Ag+(aq) + I- (aq)  AgI(s) yellow precipitate

The silver chloride dissolves in dilute ammonia to give a colourless solution:

AgCl(s) + 2NH3(aq)  [Ag(NH3)2]+ (aq) + Cl- (aq)

The silver bromide is less water-soluble, and dissolves only in concentrated ammonia to give a colourless
solution:
AgBr(s) + 2NH3(aq)  [Ag(NH3)2]+ (aq) + Br - (aq)
Silver iodide does not dissolve either in dilute or in concentrated ammonia.

The halides – reducing agents

The halide ions are reducing agents, as they can lose electrons and get oxidised:
2F-(aq)  F2(g) + 2e
2Cl-(aq) Cl2(g) + 2e
2Br-(aq) Br2(aq) + 2e
-
2I (aq) I2(aq) + 2e

Iodide ions are the most reducing, followed by bromide ions. Fluoride ions have no significant reducing
properties.
As the number of shells in the ion increases, there is more shielding of the nucleus and the outer
electrons become less strongly held. These electrons are thus lost more easily and the halide ion is more
readily oxidised.

Thus the reducing power of the halides increases down a group:

Fluoride chloride bromide iodide

Very poor reducing Poor reducing agent Fairly poor reducing Fairly good reducing
agent agent agent

Reaction of halide ions with concentrated sulphuric acid

The variation in reducing strength of the halides can be clearly seen in the reaction of the sodium
halides with concentrated sulphuric acid.

Concentrated sulphuric acid is a strong acid and can convert the sodium salts of the halides into the
hydrogen halides:
H2SO4(l) + NaX(s)  NaHSO4(s) + HX(g)
(or H2SO4(l) + X- HSO4- + HX(g))
The halide ions are not oxidised in this reaction; in fact they are behaving as bases.

Concentrated sulphuric acid is, however, also an oxidising agent; it can be reduced either to SO2, to S
or to H2S:
H2SO4 + 2H+ + 2e  SO2 + 2H2O (S reduced from +6 to +4)
H2SO4 + 6H+ + 6e  S + 4H2O (S reduced from +6 to 0)
H2SO4 + 8H+ + 8e  H2S + 4H2O (S reduced from +6 to -2)

Cl- is not a strong reducing agent so is not oxidised by H2SO4. Only the acid-base reaction takes place
and HCl gas is formed:
H2SO4 + Cl- HSO4- + HCl (acid-base reaction)

White fumes of HCl will be seen. The fumes will turn blue litmus paper red.
Br- is a better reducing agent and is oxidised, but the sulphur in the H2SO4 is only reduced from +6 to
+4 (SO2). The acid-base reaction may also take place to an extent:
H2SO4 + Br- HSO4- + HBr (acid-base reaction)
H2SO4 + 2H+ + 2Br- SO2 + Br2 + 2H2O (redox reaction)

White fumes will be seen which turn blue litmus paper red. The red/orange colour of bromine will also
be seen.

I- is a good reducing agent and is oxidised, reducing the sulphur in the H2SO4 from +6 to +4 (SO2), to 0
(S) or to -2 (H2S).The acid-base reaction may also take place to an extent:
H2SO4 + I- HSO4- + HI (acid-base reaction)
H2SO4 + 6H+ + 6I- S + 3I2 + 4H2O (redox reaction)
H2SO4 + 8H+ + 8I- H2S + 4I2 + 4H2O (redox reaction)

White fumes will be seen which turn blue litmus paper red. The purple colour of iodine vapour will also
be seen and there a will be a smell of rotten eggs due to the presence of H2S.
The reaction of halide salts with concentrated sulphuric acid

NaX observation Equation

NaCl Misty fumes (HCl)
Misty fumes (HCl)
NaBr Brown fumes, Br2
Colourless gas with
choking odour (SO2)
Misty fumes (HI)
NaI Purple fumes + black
ppt (

In the reaction with chlorides, H2SO4 acts as an acid displacing the more volatile HCl; with bromides and
iodides, the halide ions are more easily reducible and the halogen is produced as well as other products.
The reactions of the sodium salts are typical.
NaCl(s) + H2SO4(l) NaHSO4(s) + HCl(g)
NaBr(s) + H2SO4(l) NaHSO4(s) + HBr(g)
2HBr(g) + H2SO4(l) Br2(g) + SO2(g) + 2H2O(l)
NaI(s) + H2SO4(l) NaHSO4(s) + HI(g)
2HI(g) + H2SO4(l) I2(s) + SO2(g) + 2H2O(l)
6HI(g) + H2SO4(l) 3I2(s) + S(s) + 4H2O(l)
8HI(g) + H2SO4(l) 4I2(s) + H2S(s) + 4H2O(l)

The solubility of iodine (I2) in water increases with addition of KI or NaI due to the formation of
polyhalide (triiodide, I3–) ion,

However, this solution behaves as a simple mixture of KI and free I2 and contains K+ and I– ions and
free I2 molecules.

The halogens undergo some important redox chemistry.

Fluorine is such a powerful oxidizing agent that it tears water apart, oxidizing the oxygen to produce O2,
some O3 and HFO (Hypofluorous acid).

The other halogens undergo disproportionations.

Reactions of group 7 (7A, 17, the Halogens)

1. The qualitative analysis of halide ions.

The test solution is made acidic with nitric acid, which decomposes hydroxides, carbonates or
sulphites that would interfere with the test. Silver nitrate solution is then added:

Ag+(aq) + Cl- (aq)  AgCl(s) white precipitate

Ag+(aq) + Br- (aq)  AgBr(s) cream precipitate
Ag+(aq) + I- (aq)  AgI(s) yellow precipitate

The precipitates are then treated with ammonia solution. The chloride dissolves in dilute ammonia to
give a colourless solution:

AgCl(s) + 2NH3(aq)  [Ag(NH3)2]+ (aq) + Cl- (aq)

The bromide is less water-soluble, and dissolves only in concentrated ammonia to give a colourless
solution:

AgBr(s) + 2NH3(aq)  [Ag(NH3)2]+ (aq) + Br - (aq)

The iodide is even less soluble in water, and does not dissolve in ammonia at all. It may become a
paler yellow, however. The water solubility of the halide is significant because the overall
equilibrium constant for the formation of the ammine complex is the product of the equilibrium
constant for the halide solubility (the solubility product) and the equilibrium constant for the
formation of the ammine. If the first value is very small, as in the case of the iodide, the overall
constant is also very small and the iodide won't dissolve in ammonia.

2. The reaction of halide salts with concentrated sulphuric acid.

In the reaction with chlorides, H2SO4 acts as an acid displacing the more volatile HCl; with bromides
and iodides, the halide ions are more easily reducible and the halogen is produced as well as other
products. The reactions of the sodium salts are typical.

NaCl(s) + H2SO4(l)  NaHSO4(s) + HCl(g)

NaBr(s) + H2SO4(l)  NaHSO4(s) + HBr(g)

2HBr(g) + H2SO4(l)  Br2(g) + SO2(g) + 2H2O(l)

NaI(s) + H2SO4(l)  NaHSO4(s) + HI(g)

2HI(g) + H2SO4(l)  I2(s) + SO2(g) + 2H2O(l)
6HI(g) + H2SO4(l)  3I2(s) + S(s) + 4H2O(l)
8HI(g) + H2SO4(l)  4I2(s) + H2S(s) + 4H2O(l)
3. The disproportionation reactions of chlorine and chlorate(I).

Chlorine is both oxidised and reduced when it reacts with water or with sodium hydroxide solution –
disproportionation reactions.

With water: Cl2(aq) + H2O(l)  HOCl(aq) + HCl (aq)

With cold dilute NaOH solution: Cl2(aq) + 2NaOH(aq)  NaCl (aq) + NaOCl (aq) + H2O(l)

With hot concentrated NaOH solution: 3Cl2(aq) + 6NaOH(aq)  5NaCl(aq) + NaClO3(aq) + 3H2O(l)

Chlorate(I) ions on heating in solution: 3 OCl- (aq)  ClO3 - (aq) + 2Cl – (aq)

Bromine and iodine do the same thing, but the higher positive oxidation states are formed more
easily the larger the halogen.

4. The displacement reactions of halide ions by halogens.

Chlorine will displace both bromide and iodide ions; bromine will displace iodide ions.

Cl2(aq) + 2Br – (aq)  2Cl – (aq) + Br2(aq)

The reaction above is used to manufacture bromine from seawater.

Cl2(aq) + 2I – (aq)  2Cl – (aq) + I2(aq)

Br2(aq) + 2I – (aq)  2Br – (aq) + I2(aq)