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Module 2

Inorganic
Chemistry
Group 2

Ung Hie Huong


LEARNING OUTCOMES:
Students should be able to:
Describe the thermal decomposition of the nitrates, carbonates and hydroxides of Group 2
elements
Interpret qualitatively and explain the thermal decomposition of nitrates, carbonates and
hydroxides in terms of charge density and polarity of large anions
Interpret qualitatively and explain the variation in solubility of sulphates, in terms of the
relative magnitude of the enthalpy changes of hydration for the relevant ions, and the
corresponding lattice energies.

2.1 Introduction to Group 2 elements


Group 2 elements are known as Alkaline Earth Metals.
Group 2 metals: Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba).

2.2 Thermal decomposition of the nitrates, carbonates and hydroxides of Group


2 elements

Thermal decomposition Observation & Equations

Nitrates of Group 2 metals Observation(s): i. Brown fumes liberated,


(White salt, Colourless ii. Glowing splinter is rekindled
solution) iii. White residue (Metal oxide)
Products: Metal oxide, NO2 & O2

General equation: 2M(NO3)2(s) 2MO(s) + 4NO2(g) +


O2(g)
Equations:
2Be(NO3)2(s) 2BeO(s) + 4NO2(g) + O2(g)
2Mg(NO3)2(s) 2MgO(s) + 4NO2(g) + O2(g)
2Ca(NO3)2(s) 2CaO(s) + 4NO2(g) + O2(g)
2Sr(NO3)2(s) 2SrO(s) + 4NO2(g) + O2(g)
2Ba(NO3)2(s) 2BaO(s) + 4NO2(g) + O2(g)

Carbonates of Group 2 Observation(s): i. Colourless gas liberated, turns limewater


metals chalky
ii. White residue (Metal oxide)
Products: Metal oxide, CO2

General equation: MCO3(s) MO(s) + CO2(g)


Equations:
BeCO3(s) BeO(s) + CO2(g)
MgCO3(s) MgO(s) + CO2(g)
CaCO3(s) CaO(s) + CO2(g)
SrCO3(s) SrO(s) + CO2(g)
BaCO3(s) BaO(s) + CO2(g)

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Thermal decomposition Observation & Equations

Hydroxides of Group 2 Observation(s): i. Colourless gas liberated, turns blue cobalt(II)


metals chloride paper pink
ii. White residue (Metal oxide)
Products: Metal oxide, water vapour

General equation: M(OH)2(s) MO(s) + H2O(g)


Equations:
Be(OH)2(s) BeO(s) + H2O(g)
Mg(OH)2(s) MgO(s) + H2O(g)
Ca(OH)2(s) CaO(s) + H2O(g)
Sr(OH)2(s) SrO(s) + H2O(g)
Ba(OH)2(s) BaO(s) + H2O(g)

Why does the nitrates, carbonates, hydroxides and sulphates decompose to oxides
upon heating?

Oxide ion is smaller than the carbonate ion.


The nuclei distance between Mg2+ ion and O2 ion is shorter There is a stronger ionic
bond between Mg2+ ion and O2 ion Magnesium oxide has a higher lattice energy
Magnesium oxide is more stable.
The larger carbonate ion decomposes upon heating to form magnesium oxide (which is more
stable).
Oxide ion is also smaller than nitrate ion and sulphate ion Magnesium oxide is more stable
than magnesium nitrate and magnesium sulphate.

Relative thermal stabilities of Group 2 nitrates, carbonates and hydroxides

BeCO3 / Be(NO3)2/ Be(OH)2 Size of M2+ ion increases


Charge density of M2+ ion decreases
MgCO3/ Mg(NO3)2/ Mg(OH)2
Polarising power of M2+ ion decreases
CaCO3/ Ca(NO3)2/ Ca(OH)2 Ability of M2+ ion to distort anion & cause their
covalent bonds to breakdecreases
SrCO3/ Sr(NO3)2/ Sr(OH)2
Thermal stability: Increases
BaCO3/ Ba(NO3)2/ Ba(OH)2
Rate of thermal decomposition: Decreases

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2.3 Solubility of sulphates of Group 2 elements

Solubility of a substance depends on 2 factors:

1. Lattice energy (-ve)


The higher the lattice energy dissociation of compound into ions becomes more difficult
A compound with a higher lattice energy would be less soluble.
2. Enthalpy of hydration (-ve)
The higher the hydration enthalpy the easier the compound form hydrated ions
A compound with a higher hydration enthalpy would be more soluble.

Dissolution process of MSO4 (ionic solid) in water is made up of two stages:

Step 1: The ions are separated to form free gaseous ions. This involves the
breaking of the ionic bonds.
MSO4 (s) M2+(g) + SO42 (g)

Step 2: The free gaseous ions are hydrated by water to form hydrated ions.
M2+(g) + SO42 (g) M2+(aq) + SO42 (aq)

The two stages are summarized in the thermochemical cycle as follow:


2+
+ = M
- - + +
+ - - = SO42-
-
- -
+ + = H2O
+
2+ 2
M (g) + SO4 -(g)

Lattice energy Enthalpy of hydration ()


(L.E.)
+ -
- + - +
Enthalpy of solution
+ - + -
- + - + ( ) + -
2+ 2
2+
M SO4
2-
(Solid) M (aq) + SO4 -(aq)

Enthalpy of solution ( ) = L.E. +


is negative/ exothermic The compound is soluble.

is positive/ endothermic The compound is insoluble.

The more negative the value of , the more soluble the
salt.

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Solubility of Group 2 sulphates when going down the group:

Going down the group,


BeSO4 Soluble
The decrease in hydration energy is more than the
decrease in the lattice energy.
MgSO4 Soluble
Because: The size of anion (SO42) is
Sparingly much bigger than the M2+ ion. Even
CaSO4 though the size of M2+ ion increases, 2
soluble 2+ SO4
the lattice energy does not decrease
SrSO4 Insoluble very much because it depends more
on the SO42 ion (Diagram on RHS).
The enthalpy of solution becomes
less negative/ more positive/ more
2
BaSO4 Insoluble endothermic, 2+ SO4

Solubility of the sulphates


decreases.

When you descend Group 2, what happens to the


solubility of their salts?
Sulphates, MSO4 : Decreases
Carbonates, MCO3 : Decreases
Nitrates, M(NO3)2 : All are soluble

Solubility of Group 2 hydroxides, M(OH)2 and oxides (MO) when going down the group:

BeO/ Going down the group,


Insoluble
Be(OH)2 The solubility of the oxides and hydroxides increases.
The resulting solutions are alkaline.
MgO/ Sparingly
Mg(OH)2 soluble Because:
The structure of these compounds slowly changes from
CaO/ Sparingly covalent to ionic-covalent to 100% ionic.
Ca(OH)2 soluble

SrO/
Soluble You would have to refer to p5 in Module 1 if you do
Sr(OH)2 not remember the acid-base properties of oxides.
The above reason only let you have 1 mark. If more
BaO/
Soluble marks is allocated, you might want to explain this
Ba(OH)2 phenomenone with: Lattice Energy, H hydration and
H solution

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2.4 Anomalous behaviour of Beryllium (Be)

Beryllium is different from other elements in Group 2. SECOND ROW ANOMALY


How & Why? Li, Be, B, C, N, O, F
All these elements show atypical
behaviour from the heavier
elements in their respective groups.

Beryllium tends to form covalent compounds (e.g.: BeCl2), or ionic compounds with
significant amount of covalent character.

Reason 1: Beryllium atom is small.

Beryllium atom, Be Beryllium atom


r = 112 pm
4p, 4n, 4e
is SMALL.
1s2 2s2

Reason 2:
Beryllium has high effective nuclear charge (Zeff2) The two valence electrons are
tightly held.
As a result, beryllium has high 1st IE & 2nd IE Not readily ionized to form Be2+.

Reason 3:
Be2+ ion is very small Very high charge density Strong polarising power Be2+ ion
can distort the electron cloud of neighbouring anions Gives rise to covalent
character to beryllium salts.

Be2+ ion with high charge


density polarises the Polarisation of Cl ion
electron cloud of Cl ion
Be2+ Cl Be2+ Cl gives rise to covalent
character of BeCl
bond.

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BeO & Be(OH)2 are AMPHOTERIC
(not basic like other Group 2 oxides & hydroxides).
BeO(s) + 2H+(aq) Be2+(aq) + H2O(l)
BeO(s) + 2OH(aq) + H2O(l) [Be(OH)42](aq)

Be(OH)2 (s) + 2H+(aq) Be2+(aq) + 2H2O(l)


Be(OH)2 (s) + 2OH(aq) + H2O(l) [Be(OH)42] (aq)
Why?
Because BeO and Be(OH)2 are ionic-covalent.

Ionic oxides are basic.


Covalent oxides are acidic.
Ionic-covalent & covalent-ionic oxides are amphoteric.

Predict the solubility of BeO & Be(OH)2.

BeCl2 is covalent.

PROOF: Sublimes when heated.


BeCl2(s) BeCl2(g)

At r.t.p. & when dissolved in organic solvent, it exists as a dimer (Be2Cl4)


Cl
Cl Be Be Cl
Cl

Exists as polymeric chain in solid state.


Cl Cl Cl
Be Be Be Be
Cl Cl Cl

Hydrolysis of BeCl2 in water forms acidic solution.


BeCl2(s) + 2H2O(l) Be(OH)2(aq) + 2H+(aq) + 2Cl (aq)

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Form complexes:
e.g. BeCl2.2NH3
[Be(OH)4]2
BeF42
Because:
Be2+ has high charge density
Be2+ is electron deficient
Be2+ could form coordinate bonds with ligands

All the complexes have tetrahedral structure. Because


Formation of complex involves 2s and 2p orbitals
undergoes sp3 hybridization
sp3 orbitals have tetrahedal shape.

Hybridisation

2s Four sp3 orbitals


2p orbitals

Ground state Hybridised orbitals

Electronic arrangement in sp3 orbitals after complex formation:

sp3 hybridization

2.5 DIAGONAL RELATIONSHIP

It is when certain pairs of diagonally adjacent elements in Period 2 & Period 3 exhibit
the same chemical properties.

Three diagonal relationships in the periodic table:


Li & Mg; Be & Al; B & Si

Beryllium is similar to aluminium in physical and chemical properties because:


Similar atomic radii,
Similar ionic radii,
Ions have similar charge density,
Similar electronegativity.

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Both Beryllium & Aluminium:
Form oxides & hydroxides that are amphoteric

Their chlorides are covalent compounds that sublimes upon heating


BeCl2 and AlCl3 have bridged polymeric structure.
BeCl2 and AlCl3 form dimers.

Both form complexes because

Both form salts that dissolve in water to form acidic solutions

2.6 USES OF GROUP 2 COMPOUNDS

Compound Uses

MgO Refractory material in high T furnace

Mg(OH)2 @ Milk of Magnesia As antacid to relief indigestion

MgSO4 As laxative

CaSO4 Plaster of Paris

Ca(OH)2 Slaked lime used to neutralise acidic soil

CaCO3 To make writing chalks

BaCO3 Rat poison

BaSO4 As barium meal in the X-ray of digestive system