U1 M3 Group VII elements

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GROUP VII ELEMENTS

a) explain the variations in physical properties of the elements in terms of
structure and bonding (refer to volatility, density, state, only a
description of the colour is required)
b) explain the relative reactivities of the elements as oxidising agents
(include reactions with sodium thiosulphate and refer to E values, also
use solutions of the elements with bleach, bromine water and iodine
solution)
c) describe the reactions of the elements with hydrogen
d) explain the relative stabilities of the hydrides (include reference to
bond energies)
e) describe the reactions of the halide ions with:- (i) aqueous solution of
AgNO3 followed by aqueous ammonia (ii) conc. sulphuric acid
f) describe the reactions of chlorine with cold and with hot aqueous
solution of sodium hydroxide (mention changes in oxidation number)
Physical properties of halogens
All the halogens exist as diatomic molecules at room temperature. Their
melting and boiling points increase with increasing atomic number,
because the dispersion forces (van der Waals forces) between the
molecules become stronger as the number of electrons, and whereas
fluorine and chlorine are normally gases, bromine is a liquid and iodine
is a solid. The colour of the elements also deepens from almost
colourless fluorine through yellow-green chlorine and red-brown to the
deep, lustrous purple-black of iodine.
Reactivity of the halogens
Order of reactivity increases up the group.
All halogens act as oxidising agents. X(g) + e- X-(g) + (aq) X-(aq)
Strength as an oxidising agent is determined by 3 factors
1. Bond dissociation (energy needed to break the molecule into 2
atoms)
2. Electron affinities /kJ mol-1
3. Hydration energy /kJ mol-1
The first is endothermic and the last two are exothermic processes.

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The total energy change (kJ mol ) from these three processes are:fluorine -775 chlorine -607 bromine -580 iodine
-541
Since the fluoride ion shows the most negative enthalpy, it is the most
stable i.e. the most readily formed which translates to the most reactive
halogen, while iodine shows the least negative enthalpy change and this
means it is the least reactive halogen.
Reactions of the halogens with hydrogen and explanation of the
trend of thermal stability of the hydrides
H2(g) + X2(g) 2HX(g)
Fluorine:- it reacts with hydrogen gas explosively at room
temperature
Chlorine:- it reacts with hydrogen explosively only after the initiation
of the reaction by a spark or a flash of light
Bromine:- it only reacts in the presence of heat and a catalyst
Iodine:- even with the presence of heat and a catalyst, it is a
reversible reaction with the product quickly decomposing to the
starting materials
Thermal stability of the HX decreases down the group.
This can be easily explained by the trend of bond dissociation energy.
As the size of the halogen atom increases down the group, the degree of
orbital overlap becomes less extensive and thus the bond strength
decreases.
NB Acid strength increases down the group
i.e. HI > HBr > HCl >> HF

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Reaction of the halides

Table #1: Showing reaction of halides with aqueous ammonia and conc.
sulphuric acid
Reagent
AgNO3
NH3(aq)

FNo ppt
No
reaction

Conc.
H2SO4

HF(g)

ClWhite ppt
Soluble in
dilute
reagent
HCl (g)

BrCream ppt
Soluble in
conc. reagent
HBr (g) +
Br2 (g)

IYellow ppt
Insoluble in
dilute or conc.
reagent
Only I2 (g)

Reaction of chlorine with NaOH

1. With cold, dilute NaOH(aq)
Cl2(g) + 2OH-(aq) Cl-(aq) + ClO-(aq) + H2O(l)
2. With hot, concentrated NaOH (at 348K)
3Cl2(g) + 6OH-(aq) 5Cl-(aq) + ClO3- (aq) + 3H2O(l)
In reaction one, chlorine forms the chloride ion and the chlorate(I) ion.
While in reaction 2, chlorine forms the chloride ion and the chlorate (V)
ion. It is an example of disproportionation.
Worksheet

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