11.

0 The Halogens

AQA AS Specification
Lessons 1 Topics

How and why does the atomic radius and electronegativity change in Gp 7. What effect does this have on the boiling point?
To understand that the ability of the halogens (from fluorine

to iodine) to oxidise decreases down the group (e.g. the displacement reactions with halide ions in aqueous solution)
3

understand the trend in reducing ability of the halide ions know the different products formed by reaction of NaX and H2SO4

understand why acidified silver nitrate solution is used as a reagent to identify and distinguish between F- Cl- , Br- and I- know the trend in solubility of the silver halides in ammonia
know the reactions of chlorine with water and the use of chlorine in water treatment /appreciate that the benefits to health of water treatment by chlorine outweigh its toxic effects/know the reaction of chlorine with cold, dilute, aqueous NaOH and the uses of the solutions formed 2

Halogens
What are the Halogens, what does their name mean, and where are they found in the Periodic Table?

The Halogens are elements that are found in Group 7 (VII) of the PT. The name means salt former.
Name some compounds that contain a halogen What is the valency (OXIDATION NUMBER) of the halogens?

Appearance

fluorine video

Fluorine, F2, is a pale yellow gas at room temperature.

Chlorine video

Chlorine, Cl2, is a pale green gas at room temperature.

Bromine video

Bromine, Br2, is a dark red liquid at room temperature. It is the only liquid non-metal.

Bromine is volatile and readily forms a dark red vapour.

iodine video

Iodine, I2, forms shiny black crystals at room temperature.

When warmed, iodine crystals sublime (turn directly to a gas), forming a purple vapour.

Physical properties of halogens

Fluorine
What is unusual about the bonding in fluorine molecule? Explain. Compared to the other halogens, the F-F bond is very weak. This is because the fluorine atoms are very small and there is a lot of repulsion between the bonding electrons.

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Atomic Radius
The atomic radius increases down Group 7. Going down the group, there are more filled energy levels between the nucleus and the outer electrons.

This results in the outer electrons being shielded more from the attraction of the nucleus.

Boiling point
The boiling point increases down Group 7. The strength of the instantaneous dipoleinduced dipole forces between the molecules increases as the size of the molecules increases.

Trends in boiling point

Halogen molecules increase in size down the group. This leads to greater van der Waals forces between molecules, increasing the energy needed to separate the molecules and therefore higher melting and boiling points.

van der Waals forces

fluorine atomic radius = 42 10-12 m boiling point = -118 C

iodine atomic radius = 115 10-12 m boiling point = 184 C

Electronegativity
Electronegativity decreases down Group 7.

Fluorine is the most electronegative element in the periodic table.

The atomic radius increases, the outer electrons are more shielded, so bonding electrons are less strongly attracted to the nucleus. (Fig 2 p167)

Trends in electronegativity
Electronegativity of the halogens decreases down the group due to an increase in atomic radius. Increased nuclear charge has no significant effect because there are more electron shells and more shielding. Iodine atoms therefore attract electron density in a covalent bond less strongly than fluorine.

fluorine atomic radius = 42 10-12 m electronegativity = 4.0

iodine atomic radius = 115 10-12 m electronegativity = 2.5

11.2 Chemical reactions of the Halogens

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Oxidation ability
What is Oxidation? Oxidation is the loss of electrons. An oxidizing agent is an electron acceptor, the agent is reduced during the course of the reaction. This forms a redox reaction.

What is an oxidizing agent?

18

Oxidising power trend: Cl2 > Br2 > I2

When a halogen acts as an oxidising agent, it gains electrons (taken from the oxidised species). X + 2 e- 2 X2
Cl

Going down the group it becomes harder to gain an electron because:

Br

atoms are larger & there is more shielding (due to extra electron shell)

Oxidizing ability of halogens

increasing oxidizing ability
In displacement reactions between halogens and halides, the halogen acts as an oxidizing agent. fluorine

This means that the halogen:

oxidizes the halide ion to the halogen

chlorine

gains electrons is reduced to form the halide ion.

bromine

What is the order of oxidizing ability of the halogens?

iodine

Oxidizing ability of halogens

Reactions of the halogens

Halogens react with metals such as sodium and iron: halogen + sodium sodium halide They also react with non-metals such as hydrogen: halogen + hydrogen hydrogen halide They also take part in displacement reactions with halide ions, such as the reaction that is used to make bromine from potassium bromide in seawater:

chlorine +

potassium bromide

bromine +

potassium chloride

Reaction with iron

Reactions with hydrogen

The halogens react with hydrogen gas to product hydrogen halides. For example:

Cl2(g) + H2(g) 2HCl(g)

Chlorine and hydrogen explode in bright sunlight but react slowly in the dark.

Bromine and hydrogen react slowly on heating with a platinum catalyst.

Iodine combines partially and very slowly with hydrogen, even on heating.

Redox reactions of halogens

Halogen displacement reactions

Halogen displacement reactions

Halogen displacement reactions are redox reactions. Cl2 + 2KBr 2KCl + Br2 To look at the transfer of electrons in this reaction, the following two half equations can be written:

Cl2 + 2e- 2Cl-

2Br- Br2 + 2e-

What has been oxidized and what has been reduced?

Chlorine has gained electrons, so it is reduced to Cl- ions. Bromide ions have lost electrons, so they have been oxidized to bromine.

Cl2(aq)

Br2(aq)

I2(aq)

Cl(aq)

Br(aq)

I(aq)

Cl2(aq)

Br2(aq)

I2(aq)

Cl(aq)

Stays yellow solution (no reaction)

Br(aq)

I(aq)

Cl2(aq)

Br2(aq)

I2(aq)

Cl(aq)

Stays yellow solution (no reaction)

Stays brown solution (no reaction)

Br(aq)

I(aq)

Cl2(aq)

Br2(aq)

I2(aq)

Cl(aq)

Stays yellow solution (no reaction)

Stays brown solution (no reaction)

Br(aq)

Yellow solution forms (Br2 forms) Cl2 + 2 Br- 2 Cl- + Br2

I(aq)

Cl2(aq)

Br2(aq)

I2(aq)

Cl(aq)

Stays yellow solution (no reaction)

Stays brown solution (no reaction)

Br(aq)

Yellow solution forms (Br2 forms) Cl2 + 2 Br- 2 Cl- + Br2

Stays brown solution (no reaction)

I(aq)

Cl2(aq)

Br2(aq)

I2(aq)

Cl(aq)

Stays yellow solution (no reaction)

Stays brown solution (no reaction)

Br(aq)

Yellow solution forms (Br2 forms) Cl2 + 2 Br- 2 Cl- + Br2 Brown solution forms (I2 forms) Cl2 + 2 I- 2 Cl- + I2

Stays brown solution (no reaction)

I(aq)

Cl2(aq)

Br2(aq)

I2(aq)

Cl(aq)

Stays yellow solution (no reaction)

Stays brown solution (no reaction)

Br(aq)

Yellow solution forms (Br2 forms) Cl2 + 2 Br- 2 Cl- + Br2 Brown solution forms (I2 forms) Cl2 + 2 I- 2 Cl- + I2 Brown solution forms (I2 forms) Br2 + 2 I- 2 Br- + I2

Stays brown solution (no reaction)

I(aq)

11.3 halides

35

Halides
When halogens react with metals, they form compounds called halides. Many naturally-occurring halides have industrial, household and medical applications. Halide caesium chloride Formula CsCl Uses Extraction and separation of DNA Electrolysis of aluminium oxide Extraction of titanium Electrolyte in batteries Epilepsy treatment in animals

sodium hexafluoroaluminate titanium(IV) chloride lithium iodide potassium bromide

NaAlF6

TiCl4 LiI KBr

Identifying halide ions

Halides can be identified by their reaction with acidified silver nitrate solution to form silver halide precipitates.

potassium chloride

silver nitrate

potassium nitrate

silver chloride

KCl(aq) + AgNO3(aq) KNO3(aq) + AgCl(s)

Silver chloride has a low solubility in water, so it forms a white precipitate: the positive result in the test for chloride ions.

Identifying halide ions

Uses of halides in photography

Silver halides are used in photography.

Photographic film coated with a silver halide is exposed to light, causing the halide to decompose to form silver. This appears as a black precipitate on the photographic film.
Ag+ + e- Ag

light mask paper coated in silver halide

silver precipitate

white paper under mask

Hydrogen halides
The hydrogen halides are colourless gases at room temperature. Hydrogen halide HF HCl Boiling point (C) 20 -85

HBr
HI

-67
-35

Hydrogen fluoride has an unexpectedly high boiling point compared to the other hydrogen halides. This is due to hydrogen bonding between the HF molecules.

11.3 Reactions of halide ions

41

Reducing agents
What is reduction? Reduction is the gain of electrons

What happens when a Halide is used as a reducing agent? Give the half equation for the reaction

2 X X2 + 2 e
When a halide ion reduces another substance, the halide is oxidised to a halogen.

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Sodium halides and sulfuric acid

The sodium halides react with concentrated sulfuric acid. During this reaction two things can happen to the sulfuric acid. It can

be reduced

act as an acid.

The reactions of sodium halides with concentrated sulfuric acid demonstrate the relative strengths of the halide ions as reducing agents.

Sodium halides and sulfuric acid

Sodium halides and sulfuric acid

Experiment
This experiment compares how well the halides reduce H2SO4 to compare the reducing power of the halide ions. Some of the products are very toxic hence the video clips!
NaCl + sulphuric acid NaBr + Sulphuric acid NaI + sulphuric acid

Watch the clips and complete the OBSERVATIONS column in the table

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halide products

observation

reaction type

equation

Cl

Br

halide products

observation

reaction type

equation

Cl

HCl HBr

steamy fumes steamy fumes brown fumes colourless gas steamy fumes purple fumes colourless gas yellow solid gas (bad egg smell)

Br

Br2 SO2 HI I2

SO2 S H2S

Formation of hydrogen halides:

NaX + H2SO4 NaHSO4 + HX e.g. NaCl + H2SO4 NaHSO4 + HCl

Complete the final two columns of the table.

halide products

observation

reaction type

equation

Cl

HCl HBr

steamy fumes acid-base steamy fumes acid-base brown fumes colourless gas steamy fumes acid-base purple fumes colourless gas yellow solid gas (bad egg smell)

NaCl + H2SO4 NaHSO4 + HCl NaBr + H2SO4 NaHSO4 + HBr

Br

Br2 SO2 HI I2

NaI + H2SO4 NaHSO4 + HI

SO2 S H2S

Write half equations for: Cl Cl2 Br Br2 I I 2 H2SO4 SO2 H2SO4 S 2 Cl Cl2 + 2 e 2 Br Br2 + 2 e 2 I I2 + 2 e H2SO4 + 2 H+ + 2 e SO2 + 2 H2O H2SO4 + 6 H+ + 6 e S + 4 H2O

H2SO4 H2S

H2SO4 + 8 H+ + 8 e H2S + 4 H2O

halide products

observation

reaction type

equation

Cl

HCl HBr

steamy fumes acid-base steamy fumes acid-base brown fumes colourless gas steamy fumes acid-base purple fumes colourless gas yellow solid gas (bad egg smell)

NaCl + H2SO4 NaHSO4 + HCl NaBr + H2SO4 NaHSO4 + HBr 2 Br + H2SO4 + 2 H+ Br2 + SO2 + 2 H2O 2 Br + H2SO4 + 2 H+ Br2 + SO2 + 2 H2O NaI + H2SO4 NaHSO4 + HI

Br

Br2 SO2 HI I2

SO2 S H2S

halide products

observation

reaction type

equation

Cl

HCl HBr

steamy fumes acid-base steamy fumes acid-base brown fumes colourless gas steamy fumes acid-base purple fumes colourless gas yellow solid gas (bad egg smell)

NaCl + H2SO4 NaHSO4 + HCl NaBr + H2SO4 NaHSO4 + HBr 2 Br + H2SO4 + 2 H+ Br2 + SO2 + 2 H2O 2 Br + H2SO4 + 2 H+ Br2 + SO2 + 2 H2O NaI + H2SO4 NaHSO4 + HI 2 I + H2SO4 + 2 H+ I2 + SO2 + 2 H2O 2 I + H2SO4 + 2 H+ I2 + SO2 + 2 H2O 6 I + H2SO4 + 6 H+ 3 I2 + S + 4 H2O 8 I + H2SO4 + 8 H+ 4 I2 + H2S + 4 H2O

Br

Br2 SO2 HI I2

SO2 S H2S

halide products

observation

reaction type

equation

Cl

HCl HBr

steamy fumes acid-base steamy fumes acid-base brown fumes reduction of Br

NaCl + H2SO4 NaHSO4 + HCl NaBr + H2SO4 NaHSO4 + HBr 2 Br + H2SO4 + 2 H+ Br2 + SO2 + 2 H2O 2 Br + H2SO4 + 2 H+ Br2 + SO2 + 2 H2O NaI + H2SO4 NaHSO4 + HI 2 I + H2SO4 + 2 H+ I2 + SO2 + 2 H2O 2 I + H2SO4 + 2 H+ I2 + SO2 + 2 H2O 6 I + H2SO4 + 6 H+ 3 I2 + S + 4 H2O 8 I + H2SO4 + 8 H+ 4 I2 + H2S + 4 H2O

Br

Br2 SO2 HI I2

colourless gas reduction of H2SO4 steamy fumes acid-base purple fumes colourless gas yellow solid gas (bad egg smell)

SO2 S H2S

halide products

observation

reaction type

equation

Cl

HCl HBr

steamy fumes acid-base steamy fumes acid-base brown fumes reduction of Br

NaCl + H2SO4 NaHSO4 + HCl NaBr + H2SO4 NaHSO4 + HBr 2 Br + H2SO4 + 2 H+ Br2 + SO2 + 2 H2O 2 Br + H2SO4 + 2 H+ Br2 + SO2 + 2 H2O NaI + H2SO4 NaHSO4 + HI 2 I + H2SO4 + 2 H+ I2 + SO2 + 2 H2O 2 I + H2SO4 + 2 H+ I2 + SO2 + 2 H2O 6 I + H2SO4 + 6 H+ 3 I2 + S + 4 H2O 8 I + H2SO4 + 8 H+ 4 I2 + H2S + 4 H2O

Br

Br2 SO2 HI I2

colourless gas reduction of H2SO4 steamy fumes acid-base purple fumes reduction of I

SO2 S H2S

colourless gas reduction of H2SO4 yellow solid gas (bad egg smell) reduction of H2SO4 reduction of H2SO4

Reducing power trend

Cl does not reduce H2SO4
Br reduces H2SO4 from S(+6) to S(+4)

I reduces H2SO4 from S(+6) to S(-2)

Reducing power trend: Cl < Br < I

When a halide ion acts as a reducing agent, it loses electrons (given to the reduced species).
Cl

2 X X 2 + 2 e Down the group it becomes easier to lose an electron because: ions are larger & there is more shielding (due to extra electron shell)

Br

Multiple-choice quiz

Identification of metal halides

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