GROUP II
(Alkaline Earth Metals)
- Be chemistry → predominantly covalent
(it can form [Be(H2O) 4] 2+
→ Mg – Intermediate between Be and Ca → Ra
- Although the energy required to form M2+ ions are
considerably greater than those required to produce
M+ ions, it is compensated by the high LATTICE
ENERGIES in the solid salts and the HIGH
HYDRATION energies of the M2+(aq) ions.
Be2+ has a high charge to radius ratio, close to that of
Al3+ → REFER: Diagonal relationship.
Has properties that resemble Al3+:
e.g. (i) Resistance of the metal to be attacked by acids
owing to formation of an impervious oxide film
on the surface.
(ii) The oxides and hydroxides are amphoteric.
(iii) Their chlorides behave as Lewis acids.
(electron pair acceptor).
(iv) Form electron deficient hydrides.
TRENDS:
1. The following INCREASE from Ca → Ra
(i) Hydration tendencies of the crystalline salts.
(ii) Thermal stabilities of carbonates, nitrates and
peroxides.
(iii) Rates of reaction of the metals with hydrogen.
2. The following DECREASE from Ca → Ra.
(i) The solubilities of nitrates, sulphates, and chlorides
(except fluorides).
(ii) Solubility of halides in ethanol.
BERYLLIUM
EC 1s2 2s22
• Most important mineral = Beryl: [Be3 Al2 (SiO3)6]
Why is the chemistry of Be – mostly covalent?
small size,
high ionization energy and
high sublimation energy
No simple Be2+ ions. Even Be O and Be F2 have
substantial covalent character in bonding.
Be compounds are exceedingly poisonous, particularly if
inhaled, probably because Be replaces Mg in enzymes
and prevents their functioning.
BINARY COMPOUNDS
1.The oxide Be O → white crystalline solid.
- obtained by ignition of Be or its compounds in air.
- Resembles Al2 O3 and is inert.
2. Be Halides
- BeF2 obtained as a glassy hygroscopic mass by heating
(NH4)2 Be F4.
• Be Cl2} Obtained in a small scale by
• Be Br2} Direct interaction in a hot tube
• Be3 N2 – Obtained by interaction of Be with NH3 or
• N2 at 900 – 1000 oC.
COMPLEX CHEMISTRY
1. The aqua ion [Be(H2O)4]2+ occurs in strongly
acidic solutions.
- Crystalline salts may readily be formed
e.g. [Be(H2O)4] Cl2, which does not lose water over
P2O5.
Solutions of Be salts are acidic due the acidity of the aqua
ion.
Initial dissociation
[Be(H2O)4]2+ [Be(H2O)3OH]+ + H+
Thus, the ion [Be(H2O)4]2+ is highly hydrolysed in solution
than Mg → Ra.
The hydrolysis equilibria depends on the anion concentration,
temperature and pH.
• In concentrated alkaline solution the main species is
[Be(OH)4] 2- (the beryllate ion).
• The only halogeno complexes are the tetrafluoroberyllates
forming compounds such as
Pb2BeF4.
→ Be F2 readily dissolves in water to give mainly [BeF2(H2O)2].
Mg, Ca, Sr, Ba and Ra
These occur in substantial deposits, such as:
(i) Dolomite: CaCO3. Mg CO3
(ii) Carnallite: Mg Cl. KCl. 6H2O
(iii) Barytes: BaSO4
Ca = 3rd most abundant metal terrestrially
→ Soluble in liquid ammonia, though less readily
and to a lesser extent than Na.
Reactions:
(1) 2M + O2 → 2MO
(2) M + X2 → MX2 : X = F, Cl, Br, I
(3) M + S → MS
(4) 3M + N2 → M3 N2 – Be requires a markedly
higher temp (1000 oC)
(5) M + H2 → MH2 Except Be
(6) M + H2O → M(OH)2 + H2
(i) Be does not react with water
(ii) Mg forms the impervious MgO.
(7) M + 2ROH → M(OR)2 + H2
• Note: Reactions occur more readily with the heavier
members of the group.
BINARY COMPOUNDS
a) Oxides: MO
Obtained by calcinations (thermal decomposition of the
carbonate):
MCO3 (s) → MO (s) + CO2.
MgO – relatively inert, especially after ignition at
high temp.
Mg(OH)2 – insoluble in water
Ca(OH)2 → Ba(OH)2 Soluble.
a) Halides: MX2 : X = F, Cl, Br, I.
• Mg and Ca halides readily absorb water.
• Sr, Ba and Ra – halides are normally anhydrous.
• The tendency to form hydrates as well as the
solubilities in water decrease with increasing size.
(except: X = F).
REASON:
• The hydration energies decrease more rapidly
than the lattice energies with increasing size of
M2+.
• NOTE: Because of the small size of the F-
relative to the M2+ ion, the fluorides vary in
solubility in the reverse order.
• i.e.: Mg F2 < Ca F2 < Sr F2 < Ba F2
REASON:
The lattice energies decrease unusually rapidly
because the large cations make contact with each
other without at the same time making contact
with the F-.
Carbides, MC2.
• All the metals Ca → Ba or their oxides react directly
with carbon in an electric furnace to give the carbides
MC2 (Ionic acetylides).
NOTE: The compounds MCO3 are all rather insoluble in
water.
COMPLEXES:
1) Only Mg and Ca show a tendency of forming
complexes in solutions, mainly with oxygen ligands.
e.g.: in aqueous alkaline solution
Ca2+ + EDTA 4- = [Ca (EDTA)]2-
This can be used for:
(i) removal of calcium ions from water.
(ii) Volumetric estimation of Ca.
Mg and Ca halides absorb NH3 or amines affording e.g.
[Mg(NH3)6] Cl2.
ORGANOMETALLIC COMPOUNDS
Mg compounds especially Grignard reagents are the most
widely used.
Mg compounds are of two types:
(i) RMgX : X = Cl, Br, I (Grignard reagents)
(ii) MgR2
(i) RMgX – Made by direct interaction of the metal
and an organic halide (RX) in a suitable solvent,
usually an ether e.g. diethyl ether or THF.
Mg + RX → RMgX
NOTE:
(i) Reaction normally most rapid with RI, and
iodine may be used as an initiator.
(ii) For most purposes RMgX are used in situ.
(ii) MgR2 are made by the dry reaction
HgR2 + Mg (excess) → Hg + MgR2
The product is extracted using an organic solvent.
