MAIN GROUPS CHEMISTRY

Alkaline Earth Metals ( Group IIA)

 GROUP 2 ELEMENTS : ALKALINE EARTH METALS

INTRODUCTION o Be, very toxic if its

The group 2 elements comprise compounds are inhaled
beryllium, magnesium, calcium, (destroys lungs)- minor

strontium, barium and radium. element in terms of

technical importance
They follow alkali metals in the
o Mg, Ca, Sr, Ba are in
periodic table.
many common minerals and
These (except beryllium) are known
in the ocean, e.g.
as alkaline earth metals.
limestone (CaCO3),
The first element Be differs from dolomite (CaCO3∙ MgCO3)
the rest of the members and shows o Ra all isotopes of this
diagonal relationship to Al. element are radioactive
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

INTRODUCTION
 These elements have two electrons in the s -orbital of the valence
shell.
 Their general electronic configuration may be represented as
[noble gas] ns2.
 Alkali earth metal are harder, denser and stronger than alkali
metals.
 They are less reactive than alkali metals but are also too reactive to
be found in their free state in nature.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

INTRODUCTION
 Like alkali metals, the compounds of these elements are also ionic.

 mostly form ionic compounds with(highly electronegative nonmetals

found in

Groups 6 (oxides,(sulfides) and 7 (halides), as well as P((phosphides) and

N (nitrides) from Group 5 and C (carbides) from Group 4,

however, Be forms covalent compounds and Mg sometimes forms

covalent compounds
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Atomic and Ionic Radii

The atomic and ionic radii of the alkaline earth

metals are smaller than those of the

corresponding alkali metals in the same periods.

Within the group, the atomic and ionic radii

increase with increase in atomic number.

GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Ionization energies
The alkaine earth metals have low ionization enthalpies due to fairly large
size of the atoms.
Since the atomic size increases down the group, their ionization enthalpy
decreases.
The first ionisation enthalpies of the alkaline earth metals are higher than
those of the corresponding Group 1 metals.
This is due to their small size as compared to the corresponding alkali metals.
The second ionisation enthalpies of the alkaline earth metals are smaller
than those of the corresponding alkali metals.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Physical Properties
The melting and boiling points of these metals are higher than the
corresponding alkali metals due to smaller sizes.
The trend is, however, not systematic.

Because of the low ionisation enthalpies, they are strongly electropositive

in nature.
The electropositive character increases down the group from Be to Ba.

The alkaline earth metals like those of alkali metals have high electrical and
thermal conductivities which are typical characteristics of metals.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS
The atomic and physical properties of the alkaline earth metals
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Property Group IA Group IIA

(Alkali Metals ) (Alkaline Earth Metals)
Atomic radii larger smaller

Melting and boiling lower higher

point
Density lower higher

Ionization energy lower higher

Hydration energy lower higher

Lattice energy lower higher

GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Flame test
 In flame the electrons are excited to higher energy levels and when they
drop back to the ground state, energy is emitted in the form of visible light.
 Calcium, strontium and barium impart characteristic brick red, crimson
and apple green colours respectively to the flame.
 The electrons in beryllium and magnesium are too strongly bound to get
excited by flame. Hence, these elements do not impart any colour to the
flame.
 The flame test for Ca, Sr and Ba is helpful in their detection in
qualitative analysis and estimation by flame photometry.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS
Hydration Enthalpies
 Like alkali metal ions, the hydration enthalpies of alkaline earth metal ions
decrease with increase in ionic size down the group.
Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+

 The hydration enthalpies of alkaline earth metal

ions are larger than those of alkali metal ions. Thus,
compounds of alkaline earth metals are more
extensively hydrated than those of alkali metals.
 Example; MgCl2 and CaCl2 exist as MgCl2.6H2O
and CaCl2·6H2O while NaCl and KCl do not form
such hydrates.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Alkaline Earth Metal and Water

The majority of alkali earth metals produce hydroxides when reacted with water.
The hydroxides of Ca, Sr, and Ba are only slightly soluble in water; however,
enough hydroxide ions are produced to make a basic environment.
The general reaction of Ca, Sr, and Ba with water is represented below, where
M represents the metal: M(s)+2H2O(l)⟶M(OH)2(aq) +H2 (g)
Mg reacts with water vapor to form magnesium hydroxide and hydrogen gas.
Be is the only alkaline earth metal that does not react with water. This is due to
its small size and high ionization energy in relation to the other elements in the
group.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Alkaline Earth Metal Hydrides and Water

 The s-block metals form ionic hydrides when heated with hydrogen gas, for
example magnesium hydride: Mg(s) + H2(g) → MgH2(s)
which is a white crystalline solid which dissociates into Mg and H at 327oC.
However, BeH and MgH2 are intermediate/covalent.

 With the exception of beryllium (Be), the alkaline metal hydrides react with

water to produce the metal hydroxide and hydrogen gas.

 The reaction of these metal hydrides can be described below:

MH2 (s) +2H2O (l) ⟶M(OH) 2 (aq) +2H2 (g)

GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Alkaline Earth Metal and carbon

 Group 1 metals do not react with carbon, but Group 2 metals react at high
temperatures to give the metal carbides:
Ca(s) + 2C(s) → CaC2(s)
which are ionic, containing the carbide ion: (C≡C)2–.
 The carbides react with water to give acetylene gas:
CaC2(s) + 2H2O(l) → Ca(OH)2(s/aq) + C2H2(g)

 Ignited Mg metal will also react with carbon dioxide in the absence of air:
Mg(s) + CO2(g) → 2MgO(s) + C(s)
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Alkaline Earth Metal and Nitrogen

 The Group 2 metals, all except Be react upon heating:
3Mg(s) + N2(g) → Mg3N2 (s)
The nitrides react with water to produce ammonia:
Mg3N2(s) + 6H2O(l) → 3Mg(OH)2(aq) + 2NH3(g)
Magnesium nitride is a yellow or yellow-green crystalline solid which
decomposes to Mg and N2 when heated.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Oxides of the alkaline earth metals

 The reaction of Group 2 metals with oxygen is a redox reaction

2M(s) + O2(g) ==> 2MO(s) (M = Be, Mg, Ca, Sr, Ba)

 The formation of the oxide expected when the element is heated or burned

in air.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Oxides of the alkaline earth metals

 Mg-Ba form 1:1 metal oxides, MO, which crystallize with NaCl-type
structures.
 MgO is pretty insoluble in water, but the others react with water to form the
hydroxides, which tend to be insoluble.
 MgO has a melting point of 2825°C; in its crystalline form is a great thermal
conductor and a lousy electrical conductor
 When cut all the metals rapidly tarnish in air at RT, but combust when heated.
 Be and Mg tarnish in air and this oxide layer prevents further reaction.
 CaO is called “quicklime”; produced in huge quantities from calcium
carbonate (limestone)
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Oxides of the alkaline earth metals

Similarly to the alkali metal oxides, alkaline earth metal monoxides combine
with water to form metal hydroxide salts.

MO(s) + H2O(l) ==> M(OH)2(aq) (not a redox change, M = Be, Mg, Ca, Sr, Ba)

ionically: M2+O2–(s) + H2O(l) ==> M(OH)2(aq)

 The exception to this general assumption is beryllium, whose oxide (BeO)
does not react with water.

 Ionic oxides (I and II A element with O2) always react with water to give

basic solutions which increases in strength of basic character down the group.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Oxides of the alkaline earth metals

 The pH of the resulting solution ranges from ~pH 10 to ~pH 13 for

Mg(OH)2 to Ba(OH)2

 One of the most familiar alkaline earth metal oxides is CaO or quicklime.

This substance is often used to treat water and to remove harmful SO2(g) from

industrial smokestacks.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Oxides of the alkaline earth metals

All the oxides are basic and readily neutralised by acids (not a redox change).
MO(s) + 2HCl(aq) ==> MCl2(aq) + H2O(l) (M = Be, Mg, Ca, Sr, Ba)
to give the soluble chloride salt
ionically: M2+O2–(s) + 2H+(aq) ==> M2+(aq) + H2O(l)
acid proton donation to the oxide ion base.
In each case the chloride Cl–, nitrate NO3– and sulphate SO42– are spectator
ions.
MO(s) + 2HNO3(aq) ==> M(NO3)2(aq) + H2O(l) (M = Be, Mg, Ca, Sr, Ba)
to give the soluble nitrate salt
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Oxides of the alkaline earth metals

MO(s) + H2SO4(aq) ==> MSO4(aq/s) + H2O(l) (M = Be, Mg, Ca, Sr, Ba)
to form the sulphate salt (soluble => insoluble)
but reaction increasingly slower for calcium oxide ==> barium oxide as
the sulphate becomes less insoluble.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Reaction with other Group 6 elements

 In addition to forming oxides, the metals form sulphides on heating
• with sulphur (sulfur) e.g. MgS
• with selenides, e.g. MgSe

Magnesium sulphide, MgS, has the 6:6-coordinate structure of NaCl, but

much higher melting and boiling points, due to the greater ionic charges
producing stronger ionic bonding.
Mg(s) + S(s) → MgS(s)
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Alkaline Earth Metal and halogen

 All s-block metals react directly with chlorine, requiring moisture and/or
heat to initiate the reaction:
Ca(s) + Cl2(g) → CaCl2(s)

 BeCl2 is more-or-less covalent, with a low melting point.

 MgCl2 is intermediate between ionic and covalent.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Beryllium and Magnesium

Be is very small and has a high charge which makes for high charge density.
*A high charge density simply means that you have a lot of charge packed into a small volume.

• Be forms covalent bonds because of its high polarizing power.

• In the gas phase, Be is coordinatively unsaturated (electron-deficient).
• In solid phases, Be will act as a Lewis acid.
• Mg is found on the same diagonal as Li; therefore, Mg has similar properties to
Li
• Both Li and Mg are used as reagents in organic synthesis (Grignard’s reagent).
•All s-block metals except Be and Mg are stored under liquid paraffin to prevent
their reaction with oxygen. (Protective oxide layer)
GROUP 2 ELEMENTS : ALKALINE EARTH METALS
The anomalous behaviour of beryllium
 Be differs more from Mg than Li does from Na.
 Be has a diagonal relationship to Al and both elements have some behaviours
in common.
1. Be has a higher melting/boiling point, higher density and much greater
hardness than Mg.
2. Like Li, Be has a small atomic radius and higher electronegativity and
electron affinity and a higher ionisation energy.
3. The small Be2+ ion has a higher polarising power and so all or most of its
compounds are largely covalent (and so often have lower melting/boiling points
due to weak intermolecular forces).
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

The anomalous behaviour of beryllium

4. Be does not react with water and is resistant to acid.
due to a protective oxide film
Its compounds are more soluble in organic solvents.
5. Beryllium halides, BeX2, are hygroscopic solids (absorb moisture from the air)
that fume in air.
6. Beryllium is amphoteric (both basic and acidic).
7. Be is a poor reducing agent, due to its reluctance to lose its valence electrons.
8. Salts of large anions are very unstable and those that are stable are hydrated,
e.g. BeCO3·4H2O, BeSO4·4H2O,
both decompose on heating to give BeO.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS
The anomalous behaviour of beryllium
9. No peroxide or superoxide is formed.
10. Be is poisonous since it has strong complexing power with O and N-ligands.
11. When treated with acetylene, Mg forms the acetylide, MgC2, whereas Be
forms the carbide, Be2C.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

The anomalous behaviour of beryllium

12. Be compounds tend to have coordination numbers of 4.
• The ion is too small to have higher coordination numbers.
• Example;
• [Be(H2O)4]2+ occurs in hydrated beryllium salts.
• BeO has 4:4 coordination.
• In the vapour phase, the chloride contains (BeCl2)2 molecules, with
chlorines bridging between the two Be atoms.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

The anomalous behaviour of beryllium

13. BeCl2 is a covalent chain polymer, existing as dimers, Be2Cl4, in the
vapour phase, which break-up into monomers, BeCl2, at higher temperatures
(AlCl3 is similar).

*Note the halide bridge structure with the halogens arranged tetrahedrally around
each Be.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

The anomalous behaviour of beryllium

AlCl3 has a similar structure, but existing as shorter Al2Cl6 molecules held
together by weak intermolecular van der Waal’s forces.

 In the gas phase it forms Al2Cl6 dimers which break-up into AlCl3
monomers at higher temperatures.
 AlBr3 and AlI3 are similar.
GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Beryllium Oxide
 BeO has a very high melting point, making it useful for nuclear work and in
ceramics.
 BeO is amphoteric,
for example, it acts as a base in the following (slow) reaction at very low pH:
BeO(s) + H2O(l) + 2H3O +(aq) → Be(H2O)42+
in which the Be complexes with water, neutralising acid as it does so.
BeO is behaving as an acid in the following reaction:
BeO(s) + H2O(l) + 2OH–(aq) → Be(OH)42–(aq)

in which it neutralises hydroxide ions (alkali) forming the beryllate ion.

GROUP 2 ELEMENTS : ALKALINE EARTH METALS

Beryllium Oxide
 The hydroxides are not only basic, but they are alkali, an alkali being a
base which directly provides hydroxide, OH–(aq), ions on dissolving in water.
 BeO has the wurtzite structure (hexagonal crystal structure).
 A coordination number of 4
(4:4 so each Be2+ ion is surrounded by 4 of O2– ions and each O2– ion by 4
Be2+ ).
 The other Group 2 oxides have the NaCl structure (see halides) with a
coordination number of 6
(6:6, so each metal ion is surrounded by 6 oxide ions and each oxide ion by 6
metal ions).
GROUP 2 ELEMENTS : ALKALINE EARTH METALS