GROUP 2 ELEMENTS
(ALKALINE EARTH METALS)
Elements of Group 2 are:-
Beryllium-Be; Magnesium-Mg; Calcium-Ca; Strontium-Sr; Barium-Ba & Radium-Ra.
They are called alkaline earth metals because their earths (earth is the old name for a
mineral oxide) are alkaline in nature. However, beryllium is not counted as an alkaline
earth metal since its earth is not alkaline.
Like the group 1 elements, they show a distinct group relationship in which similarities
between the elements are more pronounced than the differences between them. The first
member of the group is ‘anomalous’ (cf. lithium).
Table 1: Some properties of the alkaline earth metals
Properties Be(4) Mg(12) Ca(20) Sr(38) Ba(56) Ra(88)
Electron [He]2s2 [Ne]3s2 [Ar]4s2 [Kr]5s2 [Xe]6s2 [Rn]7s2
configuration
IE KJmol-1 900 736 590 549 503 508
1st
IE 2nd 1762 1450 1146 1064 960 975
EN (Pauling) 1.5 1.2 1.0 1.0 0.9 -
Std redox -1.85 -2.37 -2.87 -2.89 -2.90 -2.92
potential (V)
Ionic radius Ao 0.31 0.65 0.94 1.10 1.29 1.50
Hhydr (eV) -24.8 -20.2 -16.6 -15.2 -13.7 -
M.pt oC 1280 651 845 789 725 700
B.pt oC 2970 1107 1487 1380 1640 1140
Density(g/cm3) 1.85 1.75 1.55 2.6 3.62 5.5
Hardness decreasing
Reactivity increasing
Basicity increasing
Occurrence
The alkaline earth metals, like alkali metals are very reactive, therefore, do not occur free
in nature. All of them are found in the form of their salts. These metals are strong
reducing agents (though not as good as the alkali metals) and, therefore, it is very
difficult to obtain them by chemical reduction methods.
Magnesium (2.76%) and calcium (4.66%) are among the eight most abundant elements in
the earth’s crust. In sea water magnesium (0.13%) is the second most abundant metallic
element next only to sodium. Calcium occurs extensively as calcite and lime-stone
(CaCO3) in many mountain ranges. Strontium (0.038%) and Barium (0.039) are much
less abundant and occur as carbonates and sulphates. These metals are well known
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because they occur as concentrated ores and are easy to extract. Radium is extremely
scarce and it is a radioactive element.
Physical properties
1. They loose ns2 electrons to form divalent cation M2+ according to their electronic
configuration.
2. They are soft, but harder than the corresponding Group 1 elements because of their two
valence electrons which participate in metallic bonding.
3. They are denser and have higher m.pts & b.pts than alkali metals.
4. Their redox potential is comparable to Group 1 because of their higher hydration
energy which compensates for IEs. Be redox potential is exceptional because of the
high IE it possesses due to its small size.
5. Their compounds are less ionic than the alkali metals because of their polarizing power
due to their high charge density.
6. Despite of having high hydration energies their salts are less soluble than those of the
Group 1 metals. This is due to the even higher lattice energies which overcompensate
hydration energy.
Chemical properties
Group 2 metals are less reactive than alkali metals as they are less electropositive than the
latter. However, the reactivity increases down the group.
Oxides and hydroxides
All metals burn in air when heated and form normal oxides:
Heat
2M(s) + O2(g) 2M2+O2-(s)
Ba & Ra form some peroxide.
All oxides are basic (except BeO) and react with water to form hydroxides
MO(s) + H2O(l) M2+(OH-)2(aq)
Be(OH)2(s) is solid and amphoteric
BeO(s) + H2O(l) + 2H3O+(aq) Be(H2O)42+4(aq)
BeO(s) + H2O(l) + 2OH-(aq) Be(OH)42-4(aq)
Reaction with water
All group 2 metals react with water less readily than alkali metals to give hydrogen and
metal hydroxides.
M(s) + 2H2O(l) M(OH)2(s) + H2(g)
2
Be does not react with water or steam even at red heat. Mg reacts with hot water; and Ca,
Sr and Ba react with cold water.
Reaction with non-metals
1. Hydrides
React with hydrogen at higher temperatures
M(s) + H2(g) MH2(s)
Mg reacts only under pressure, Be does not react at all. However, Beryllium hydride
can be formed by reducing beryllium chloride with LiAlH4. CaH2, SrH2 and BaH2 are
ionic. BeH2 and MgH2 are covalent and polymeric. (BeH2)n has an interesting structure.
The polymeric solid contains hydrogen bridges between beryllium atoms.
H H H
Be Be Be Be
H H H
Beryllium hydride polymer
Each Be atom is bonded to four hydrogen atoms and each hydrogen atom forms two
bonds as it is bridging two Be atoms. Since Be has two valence electrons and H only one,
it is apparent that there are not enough electrons to form the usual electron pair bonds in
which two electrons are shared between two atoms. Instead of this, three centre – two
electrons bonds are formed in which a ‘banana – shaped’ molecular orbital covers three
atoms Be…H…Be, and contains two electrons. The monomeric BeH2, if formed with
normal bonds, would have only four electrons in the outer shell of the Be atom and would
be electron deficient. This would make the molecule very unstable; that is why BeH2
exists as a polymer.
2. Halides
React with gaseous halogens to form halides
M(s) +X2(g) MX2(s)
Be halides are covalent and other halides are ionic. Be halides are hygroscopic and fume
in air due to hydrolysis. They sublime and do not conduct electricity. Other halides are
also hygroscopic but they form hydrates e.g. CaCl2.6H2O.Anhydrous Be halides are
polymeric solids and can be represented as (BeCl2)n as (BeH2)n above.
3. Sulphides
React explosively when warmed with sulphur powder.
Warm
M(s) + S(s) MS(s)
These sulphides are sparingly soluble in water and are hydrolysed
MS(s) + 2H2O(l) H2S(g) + 2MOH(aq)
4. Nitrides
React with nitrogen at red heat
3M(s) + N2(g) M3N2(s)
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The stability decreases on descending the group. Vigorous hydrolysis of these
nitrides with water yields ammonia.
5. Carbides
React with carbon at higher temps to form ionic carbides. Stable ones are Ca, Sr & Ba.
Very high temp.
M(s) + 2C(s) MC2(s)
Complex formation
Complex formation is favoured by small, highly charged ions (having a high charge
density) with empty orbitals suitable to accept dative bond electrons from ligands.
Since their ions are smaller and more highly charged, the Group 2 metals form more
complexes than Group 1 metals and mostly with ligands in which halogens, oxygen or
nitrogen atoms donate electrons thus forming dative bonds with them.
Within the group the ability to form complexes decreases with the increase in size of the
metal ions. Thus Be forms most complexes while Ba forms very few.
Be forms complexes with tetrahedral arrangement because of the available orbitals as
shown below:
1s 2s 2p
Be atom in No unpaired electrons so no
ground state covalent bonds
Be atom in Two unpaired electrons can
excited state form two covalent bonds
Two fluoride ions each donate an
Be in [BeF4]2- electron pair into an empty orbital
forming a coordinate bond
sp3 hybridisation
The well known tetrafluoroberyllates [BeF4]2- have a tetrahedral structure shown below.
Beryllium forms white crystalline molecular oxide-carboxylates, of which basic
beryllium acetate, viz., [OBe4(CH3COO)6] is typical and important for the purification
of Be because of its volatility and solubility in organic solvents. Be forms a number of
chelates also with ligands like oxalates, [Be(C2O4)2]2- and –diketonate anions.
Magnesium forms a very important complex occurring in nature, chlorophyll; a green
pigment of the plants which produces sugars for the plant in the presence of sunlight, CO
and H2O in a process called photosynthesis.
Chlorophyll
6CO2 + 6H2O Sunlight C6H12O6 + 6O2
Glucose
Mg in chlorophyll is coordinated by four nitrogen atoms in the heterocyclic porphyrin
ring system.
The rest of the elements from Ca to Ba form complexes only with strong complexation
agents such as acetylacetone, ethlenediaminetetraacetic acid (EDTA), etc. E.g.
Ca2+ + EDTA4- = [Ca(EDTA)]2-
4
2-
Be
F
F
Tetrafluoroberyllate complex ion. [BeF4]2-
Organometallic compounds
The organic derivatives of Be and Mg are more covalently bonded (alkyls & aryls); while
the organo derivatives of Ca, Sr and Ba are ionic in nature.
The most useful of the organometallic derivatives is the so called ‘Grignard reagent’, the
mixture formed when Mg metal reacts with organic halides in ether solution.
(C2H5)2O
RX + Mg RMgX
The Grignard reagents (alkyl and aryl Mg Halides) are so well known on account of their
uses in synthetic organic chemistry and are also useful intermediates for the preparation
of a variety of other Organometallic compounds by halogen – exchange reactions.
Mg compounds are of the types RMgX (Grignard reagents) and MgR2. They are:-
1. Reactive
2. Sensitive to oxidation by air
3. Sensitive to hydrolysis by water.
Organoberyllium alkyls are:-
1. Liquids or solids of high reactivity
2. Spontaneously flammable in air
3. Violently hydrolysed by water.
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Solubility of Alkaline-Earth Metals in Liquid Ammonia
The properties of the solutions formed when Group 2 metals dissolve in liquid ammonia
parallel those of the alkali metals. I.e. Optical behaviours; conduction of electricity and
magnetic properties.
Group 2 metal atoms dissolve and loose two electrons:-
M(s) + (2x + y)NH3 M(NH3)y2+ + 2e(NH3)x- -----------------------Eqn (1)
Attempts to dissolve Mg in pure ammonia give no indication of forming a blue solution;
rather upon prolonged contact with boiling ammonia, hydrogen is evolved. However, if a
strong base such as NaOCH3 or KNH2 is present, a blue solution readily forms. This is
because Mg2+ has a relatively high charge density, thus, if any Mg does dissolve
according to Eqn (1), the Mg2+ formed interact strongly with the solvent to give
ammonolysis products:-
Mg(NH3)x2+ + NH3 Mg(NH3)x-12+ (NH2)- + NH4+ ---------------Eqn (2)
Thus, the dissolution of Mg would produce solvated electrons [Eqn (1)] and NH4+
[Eqn(2)] which would react to form hydrogen:-
NH4+ + e(NH3)x- (x+1)NH3 + ½H2 -------------------------------Eqn (3)
In the presence of a strong base the equilibrium in Eqn (2) can be suppressed to the point
where the NH4+ concentration is negligible. Under these conditions the reaction described
by Eqn (3) does not occur and the solution turns blue.
In the case of calcium, evaporation of the metal-ammonia solutions yields a substance
with the formula Ca(NH3)6.
Note: Be does not dissolve in liquid ammonia.
BERYLLIUM: Covalence and Stereochemistry
Because of the small size, high IE and high sublimation energy of Be, its lattice energy
and hydration energies are insufficient to provide complete charge separation and the
formation of simple Be2+ ions. Thus, even in compounds with the most electronegative
elements such as BeF2 and BeO, there appears to be substantial covalent character in the
bonding. On the other hand, for the formation of two covalent bonds —Be— , it is clear
that unpairing of the two 2s electrons is required i.e. formation of sp hybrid orbitals and
the X—Be—X system is linear.
Be in condensed phases achieves maximum four-fold coordination by:-
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1. Polymerization occurs through bridging as in sold BeCl2 below [e.g. in (BeF2)n,
(BeCl2)n or {Be(CH3)2}n]
X X X
X X
... Be Be Be Be ...
X X
X X
X
each Be atom achieves a coordination number of four.
2. By functioning as a Lewis acid
(a) Interaction of BeX2 as a Lewis acid with solvents to give four coordinated
compounds like Cl2Be(OR2)2, BeCl2(OEt2)2
(b) Interaction of BeX2 with anions/ligands to give anionic species or complex ions such
as BeF42- and [Be(H2O)4]2+
3. Formation of a covalent lattice in binary compounds like BeO or BeS which have the
wurtzite (ZnO) or Zinc blende (ZnS) structures.
USES
Uses of elements
Beryllium:
Be is an expensive metal, but it has some special characteristic to make it useful.
• Used for making atomic fuel containers because it absorbs very few neutrons and
does not become radioactive.
• Being transparent to X-rays, it is used as a window material in X-ray apparatus.
• Be is also a moderator of neutrons (that is it slows them down) and is used in
nuclear reactors and weapons.
• It has a number of uses as alloys, e.g. when mixed with Cu, Be increases the
strength of Cu sixfold. It gives an alloy as hard as steel. The alloy is used to make
non-sparking electrical conductors contacts. Therefore, these are used in making
hand tools for use in the petroleum industry.
Note:
Special conditions must be taken when working with beryllium and its alloys
as the metallic dust is very toxic. (Be compounds are also very toxic)
Magnesium:
Commercially, the most important group IIA metal is magnesium.
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• It is used in large quantities to make aluminium alloy, to which it imparts
hardness as well as corrosion resistance. The alloy appears to gain corrosion
resistant from each metal. Mg is resistant to bases (but dissolves in acids); Al is
somewhat resistant to acids (but dissolves easily in bases). Similarly Mg alloys
often contain small quantities of Al. These alloys are especially used in aircraft
and missile industry, where lightness is required. They are also used to make such
things as truck bodies, auto parts and ladders.
• Photographic flash lamps use a fine Mg wire in oxygen and give off a brilliant
white light when the metal burns.
• Mg is used as a reducing agent in the extraction of some metals like titanium and
uranium. It forms Grignard reagent, RMgX, which are important reagents.
Calcium:
• Is used as a scavenger (agent used to remove impurities in materials) in the
production of certain metals and in preparing various alloys.
• When added to lead, it produces a hard metal for storage battery grids
(electrodes).
• Used also as a reducing agent in preparing some of the less common metals, such
as thorium:
ThO2(s) + 2Ca(l) Th(s) + 2CaO(s)
1000 oC
Barium:
• Is used in small amounts in the manufacture of television and vacuum tubes to
remove traces of air.
Note:
Ca, Sr and Ba as free metals do not find extensive uses because they are very
reactive.
Uses of compounds
Compound Use
MgO Refractory bricks (for furnaces); Animal feeds.
Mg(OH)2 Source of Mg for the metal and compounds; Milk of magnesia
(antacid & laxative)
MgSO4.7H2O Fertilizer; Medicinal uses (laxative & analgesic); Mordant (used in
dyeing fabrics)
CaO & Ca(OH)2 Manufacture of steel; Neutralizer for chemical processing; Water
treatment; Mortar; Stack-gas scrubber (to remove H2S & SO2)
CaCO3 Paper coating & filler; Antacids; Dentifrices
CaSO4 Plaster; Wallboard; Portland cement
Ca(H2PO4)2 Soluble phosphate fertilizer
BaSO4 Oil-well drilling mud; Gastrointestinal x-ray photography; Paint
pigment (lithopone)
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