iv)

v)
Li + 4NH,
2Li + CI,
-
- [Li(NH,),]++ e
ZL~CI.
Alkali Metals

10. The most stable complexes would be formed by the highly polarising cations. Li' being
the most polarising cation of all the alkali metals, forms larger number of complexes
than the other Group 1 metals.
Periodicity and s-Block
Elements UNIT 5 ALKALINE EARTH METALS
Structure
5.1 Introduction
Objectives
5.2 Occurrence, Extraction and Uses
5.3 General Characteristics
Physical Properties
Chemical Properties
ComplexationBehaviour
5.4 Anomalous Nature of Beryllium
5.5 Summary
5.6 Terminal Questions
5.7 Answers

5.1 INTRODUCTION
In the previous unit, you studied the general characteristics of Group lelements, i.e., alkali
metals and their compounds. Group 1 and Group 2 elements belong to the s-block of the
periodic table, as they have ns' and ns2 outer shell electronic configuration, respectively.
s-Block elements are known to be very reactive metals and generally form ionic compounds
In this unit you will study the elements of Group 2 consisting of beryllium, magnesium,
calcium, strontium, barium and radium. Elements Ca, Sr, Ba and Ra 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 1elements, 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. lithiu'm). In this unit, we will study the
general characteristics and chemistry of this group of elements.

Objectives
After studying this unit you should be able to:
describe the general trend in the properties of the Group 2 elements,
explain chemistry of the Group 2 elements,
correlate the complexation behaviour of these elements, and
explain why and how beryllium differs from the rest of the members of the group.

5.2 OCCURRENCE, EXTRACTION AND USES

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 and, therefore, it is very difficult to obtain them by chemical reduction methods. All
of these find some or the other use in industry. Let us now study their occurrence, extraction
and uses in this section.
Occurrence
Beryllium, the first member of the group is found in small quantities in the silicate mineral,
The gem stone, emerald, beryl, phenacite, Be2Si0, and beryl, 3Be0.A120,.[Link] (2.76%) and calcium (4.66%)
the green colour bang due to the are among the eight most abundant elements in the earth's crust. Magnesium (0.13%) is the
presence of chromium. second most abundant metallic element next only to sodium (chloride) in sea water. It
occurs as magnesite, MgCO,; dolomite, MgCa(CO,),; kieserite, MgSO,.&O and camallite,
KMgC1,.6H20 in the earth's crust. Calcium &curs extensively as calcite and lime-stone
(CaCO,) in many mountain ranges. Calcium and magnesium are very important biologically
too. Calcium is found in the bones of animals and human beings. Magnesiuniis found in the
green pigment, viz., chlorophyll of the plants. Strontium (0.038%) and barium (0.039%) are
much less abundant and occur as carbonates and sulphates: These metals are well known
because they occur as concentrated ores a d are easy to extract. Radium is extremely scarce .
(10-lo%) and it is a radioactive element.
Extraction Alkaline Earth Melals
These metals are extracted by electrolysis of their fused chlorides, though magnesium has ,

been manufactured by the carbon reduction of its oxide also. Thus, beryllium is obtained by
the electrolysis of molten beryllium chloride. However, sodium chloride must be added to
the melt as an electrolyte because BeCl, is covalent and, therefore, is a very poor electrica!
conductor. During the electrolysis, the less active metal, Be, is produced at the cathode and
Cl, is evolved at the anode. Calcium is extracted from fused calcium chloride using anode of
and cathode of iron. Strontium chloride and barium chloride are used for the
extraction of strontium and barium, respectively.
Uses
Beryllium is 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. It has a number of uses as alloys, e.g., when mixed with Cu, Be
increases the strength of Cu sixfold. Beryllium alloys are non-sparking, therefore, these are
used in making hand tools for use in the petroleum industry. Magnesium, because of its
lightness, is used as a construction alloy material, e.g., in aircrafts. For this purpose, it is
alloyed with aluminium. Magnesium is used as a reducing agent in the extraction of some
metals like titanium and uranium. It forms Grignard reagents, RMgX, which are important
organic reagents calcium, stronuum and barium as tree metals do not find extensive uses
because they are very reactive. Calcium oxide (quick lime) is a constituent of glass, mortar
and portland cement. Thus, it finds extensive use in industry.
Mme. Marie Sklodowska Curie,
1867-1934. She got Nobel Prize

5.3 GENERAL CHARACTERISTICS isolating

in 1911 for
radium.
discovering and

All the Group 2 elements have two electrons in their outermost orbital. Their outer orbital
electronic structures may be written as 2s2,3s2, 4s2, 5s2,6s2 and 7s2for Be, Mg, Ca, Sr, Ba
and Ra, respectively. Because of their similar outermost electronic configuration, they show
more or less similar properties. However, beryllium being the first element of the group,
shows considerable differences from the rest of the elements of the group and exhibits
diagonal relationship with aluminium in group 13. In this section we will discuss in brief the
physical and chemical properties, solubility and complexation behaviour of these elements.

5.3.1 Physical Properties

The alkaline earth metals are quite soft metals, but are harder than the corresponding
Group 1 elements. This is because of their two valence electrons which participate in metallic
bonding. i hey are good conductors of electricity. In pure form they are silver coloured, but
on exposure to atmosphere, the silvery lusture is lost, because of the formation of oxide
layer on the surface of the metal. Their physical properties are given in Table 5.1.
Table 5.1: Properties of the Group 2 metals

Property Beryllium Magnesium Calcium Strontium Barium Radium

Be Mg Ca Sr Ba Ra

Atomic Number 4 12 20 38 <6 88

Electronicconfigurat~m [He]2sZ [Ne]3sZ [Ar]4sZ [Kr]5s2 [Xe]6sZ [Rn]7sZ
Atomic weight 9.012 24.312 40.08 87.62 137.34 226.02
Ionic radius (pm) 31 65 99 113 135
Covalent radius (pm) 89 136 174 191 198
Boiling pomt (K) 3243 1380 1760 1607 1413 1700
Melting pant (K) 1553 934 1118 1062 998 700
Enthalpy of hydration -2455 -1900 -1565 -1415 -1275
(kJ mol-')
Density (10' x kg m-?) 1.85 1.74 1 54 2.6 3.62 5.5
Electronegativity 1.5 1.2 1.0 1.O 0.9 0.9
Ionisation energy (LJ mol ') 1 900 738 590 549 502 509

r I1 1757 1450 1146 1064 965 975

The atoms of the alkaline earth metals are smaller than those of the corresponding Group 1
elements. This is because of the increase in effective nuclear charge with the increase in
Periodicity and s-Block atomic number. Due to increase in effective nuclear charge, vdience shell electrons are
Elements pulled in more firmly by the nucleus, thereby reducing the size of the arc,:;. alniilarly. their
ionic radii are also smaller than those ofGroup 1 elements, because the removal of two
orbital electrons increases the effective nuclear charge even further.
These elements are denser than Group 1metals because they have two valence electrons per
atom for bonding the atoms into a metallic lattice and as a result more mass can be packed
into a smaller volume. The density decreases slightly on moving down the group from Be to
Ca but increases considerably thereafter up to Ra.
The atomic and ionic radii increase from Be to Ra due to the effect of extra shells of
electrons being added. This outweighs the effect of increased nuclear charge.
Group 2 metals have higher melting points when compared to the Group 1 metals. The
reason being +2 charge on the cations in the metallic lattice, causing them to be more
strongly attracted to the 'sea of electrons' and making it difficult to pull them apart.
The first ionisation energy (Table 5.1) of alkaline earth metals is more than that of
corresponding alkali metals. This is because the alkaline earth metals have higher effective
nuclear charge and are smaller in size, thereby the electrons are more tightly held to the
nucleus. The second ionisation energy of these elements is almost twice their first ionisation
energy. This is because once one electron has been removed, the effective nuclear charge
Lower second ionisation energies of felt by orbital electrons is increased, so that the remaining electro~sare more tightly held
the alkaline earth metals as
and hence, much more energy is needed to remove the second electron. However, their
compared to those of alkali metals
can be exemplified as below: second ionisation energy is less than that of the corresponding alkali metals because of
stability of a closed shell configuration of the univalent cations that are formed in the latter
Mg -t Mg++ e (Electronic cases. The ionisation energy of alkaline earth metals also decreases on moving down the
(2,8,2') (2.8.1) configura-
group.
Mg+ -, Mg+++ e tion of the
(2.8.1) (2,8) metal and The metals of this group (beryllium is an exception) form ionic compounds. This is because
stable the ion is the assembly of positive and negative ions into a symmetrical crystal lattice results i~ the
closed given in
shell brackets.) liberation of a large amount of energy. As a result of the exothermic process (refer to Born
Na Na++e Haber Cycle, Unit 3 of Atoms and Molecules course), there is the overall formation of
(2;8,1) (2.8) ionic compounds.
Na+ -, Na" + e
(2.8) (2.7) Electropositive character and the reducing property (tendency to lose electrons) increase on
stable moving down the group.
closed
shell As the alkaline earth metals may lose electrons quite easily, they form divalent cations
which have a noble gas structure with no unpaired electrons. Therefore, their compounds are
diamagnetic and colourless, unless the anion is coloured. Ca. Sr and Ba compounds give
characteristic flame colourations which are used to identify them -Ca (brick red flame), Sr
(crimson red flame) and Ba (apple green flame).
SAQ 1
Write answers for the following questions in short in the given space.
a) Why are Group 2 elements smaller in size than their counterparts of Group l ?

b) Why are Group 2 metals harder and have higher melting points as compared to the
Group 1 metals?
.......................................................................

'
Solubility, Lattice Energy and Hydration Energy
We observe some interesting trends in the solubility of alkaline earth metal compounds. The
metal ions are easily hydrated, e.g., MgC1,.6$O, CaC1,.6%0, BaC4.240. The hydration
energies of these ions are much greater than those of alkali metal ions (Table 5.2), because
of their smaller size and increased cationic charge (see Unit 4, Sec. 4.3). The lattice energies
 (Table 5.2) of alkaline earth metal salts are also much higher than those of alkali metal salts. Alkaline Earth Metals
Hydration and lattice energies decrease with increase in size of metal ions. Decreasing
lattice energy favours increased solubility, whilst decreasing hydration energy favours
decreased solubility. If on moving down a group the hydration energy decreases more
rapidly than the lattice energy, the compound becomes less soluble. This occurs with most
of the compounds except for fluorides and hydroxides, for example, solubility of sulphates
decreases from BeSO, to BaSO,. Due to their small ionic radii, Be2+and Mg2+have high
hydration energies. Thereby BeSO, and MgSO, are soluble in water. CaSO, is only slightly For a substance to dissolve, the
soluble in water, whereas SrSO, and BaSO, are almost insoluble in water. In case of hydration energy must exceed the
fluorides and hydroxides, the lattice energy decreases more rapidly than their hydration lattice energy
energy. This causes a reverse trend, i.e., the fluorides and hydroxides increase in solubility
on moving down the group.
5.2: Enthal~iesof hydration, M,,, of alkaline earth metal ions, M2+and lattice energies, mb,
of their oxides, carbonates, fluorides and iodides in kJ mol-1

Mb
F d

M2+ MO MCO, MF~ M4

Be -2494 - - - -
Mg -1921 -3923 -3178 -2906 -2292
Ca -1577 -3517 -2986 -2610 -2058
Sr -1443 -33 12 -27 18 -2459 -
-
Ba -1305 -3120 -261 4 -2367 -

SAQ 2
On the basis of the data given in Table 5.2 predict the solubility behaviour of alkaline earth
carbonates. Ar13werin about 60 wbrds.
............................................. .............................
...........................................................................
..........................................................................
..........................................................................
5.3.2 Chemical Properties
You studied in the earlier sections about some of the physical properties ofGroup 2
elements. Let us now see how they behave chemically.
A few of the chemical reactions shown by alkaline earth metals are given in Table 5.3.
These metals are less reactive than alkali metals as they are less electropositive than the
latter. However, the reactivity increases with increasing atomic number down the group.
Table 5.3: Reactions of the Group 2 metals
.
2 ~ ( s+)O,(g) -+ 2MO(s) All bum if heated. Some MO, formed.
M(s) + S(s) -iMS(s) The sulphides are insoluble, but hydmlyse if heated in
water.
M(s) + 2H20(0 + M(OH),(s) + q(f? Be does not react even at red heat; Mg reacts with steam
only; others react with water at room temperature.
M(s) + 2H(aq) + MZ+(aq)+Hz(&!) Be only slowly; others more quickly.
M(s) + H,dp) -i M2+2HW Not with Be. With others at high temperaturesonly. With
Mg under pressure.
M(s) + X,W -+ MX,(s) X =halogen.
No polyhalides are formed.
3 W ) + N,(g) -t M,N,(s) At red heat. Stability: Be > Mg > Ca (hydmlyse to W,).
3M(s) + 2NH,(g) + M,N,(s) + 3H,(g) In liquid ammonia, Ca, Sr. Ba give blue solution because
of solvated electrons (Unit 4, Section 4.4).
BC + ZH20+10H -+ lBe(OH),l2-+ Hz(d Not with other alkaline earth metals.
. M(s) + 2Cts) + MC,(s) At high temperatures Be forms Be$ Ionic compounds.

All the metals liberate hydrogen from acids, although bejlllium reacts slowly. Beryllium
also likrates hydrogen when treated with sodium hydroxide solution. The reaction can
be given 3s: 75
I'eriodicity and s-Block Be + 2H20+ 2 0 H -> [Be(OH),12-+ H,(g)
Elenie~itv
This explains the anomalous behaviour of beryllium, in having amphoteric properties.
All the alkaline earth metals bum in oxygen to form oxides, MO. The oxides are d . ; ~
formed by thermal decomposition of MCO,, M(OH)?,M(NO,)? and MSO,. Berylliunl
oxide is covalent and all other oxides are ionic in nature. Be0 has wunzite (hexagonal
ZnS) structure (Fig. S.l),each ion has four nearest neighbours distributed tetrahedr:~lly
around it. Others have sodium chloride type of structure, i.e., each metal ion, M". is
surrounded by six 02-ions and each 02-is surrounded by six metal ions (Fig. 5.2). CaO is
prepared on a large scale by heating calcium carbonate in lime kilns and is used in the
manufacture of sodium carbonate, calcium carbide, bleaching powder, glass and cement.

Fig. 5.1 :Wurtzite (ZnS) structure Fig. 5.2: Rock salt (NaCI) structure

Barium peroxide, BaO,, is formed by passing air over heated BaO, at -800K, strontium
peroxide, SrO,, is obtained in a similar way at high temperature and pressure. Calcium
peroxide, CaO,, is obtained as a hydrate by treating Ca(OH), with hydrogen peroxide,
H,O,, and then dehydrating the product. Magnesium peroxide, MgO,, is obtained only in
the crude form by using hydrogen peroxide, but no peroxide of beryllium is known.
These peroxides are ionic solids having (0-0)'- ion and can be considered as salts of very
weak acid, H,O,. The peroxides on treatment with dilute acids form H,O,.
Alkaline earth metals react with water less readily than alkali metals to give hydrogen
Stalactite: The downward growth and metal hydroxides. Beryllium does not react with water or steam even at red heat.
of CaCO, formed on the roof of a Magnesium reacts with hot water and Ca, Sr and Ba react with cold water to form the
cave by the trickling of water corresponding hydroxides. Beryllium hydroxide, Be(OH),, is amphoteric; the basic
containing calcium compounds.
strength increases in the order Mg to Ba. Aqueous solutions of calcium and barium
Stalagmite: The upward growth hydroxides are known as lime water and baryta water, respectively. Ca(OH), reacts with
from the floor of a cave; of the CO, to form first an insoluble CaCO, whichfurther reacts with CO, to give soluble
same nature and origin as a bicarbonate.
stalactite.
Ca(OH), + CO, CaCO, J+ H,O
----+
(insoluble
white ppt.)
CaCO, + COZ+ H,O ---+ Ca(HCO,),
(soluble)
Calcium and barium bicarbonates are stable only in solution and decompose on removal of
water to give carbonates. This property of bicarbonates is the reason for stalactite and
stalagmite formation (Fig. 5.3).
Metal halides, MX,,are obtained by direct combination with halogens as well as by the
action of halogen acids on metals. Beryllium halides are covalent and other metal halides
are ionic. Beryllium halides are hygroscopic and fume in air due to hydrolysis. They
sublime and do not conduct electricity. Anhydrous beryllium halides are polymeric.
Beryllium chloride vapours contain BeCI, and (BeCl,),, but the solid is polymerised and
can be represented as (BeCl,),, (Fig. 5.4).
 ,\lk:~liz: I ; ~ r f hMetals

Sublimation is the conversion of a

solid directly into vapour and
subsequent condensation back to
the solid. It occurs for a substance
when at a partic~ilarpressure, its
b.p. is lower than its m.p.

Fig. 5.3: The growth of stalactites and stalagmites (Cheddar Cave)

(c)
Fig. 5.4: Beryllium chloride. (a) monomer (b) dimer and (c) polymer

The halides are hygroscopic and form hydrates. CaCI, is a well known drying agent and
anhydrous MgCI, is important in the electrolytic extraction of Mg.
All the Ciroup 2 elements except beryllium form hydrides, MH,, by direct combination
with hydrogen. Beryllium hydride can be formed by reducing beryllium chloride with
lithium aluminium hydride, LiAlH,. All these hydrides are reducing agents which react
with water and liberate hydrogen. Calcium, strontium and barium hydrides are ionic and
contain the hydride ion, H-. Beryllium and magnesium hydrides are covalent and
polymeric, (BeH,)" has an interesting structure. The polymericsolid contains hydrogen
bridges between beryllium atoms, (Fig. 5.5).

Fig. 5.5 :Beryllium hydride polymer

Each beryllium atom is bonded to four hydrogen atoms and each hydrogen atoms 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 bonds are formed
in which a 'banana-shaped' molecular orbital covers three atoms Be ...H...Be, and contains
two electrons. The monomeric molecule BeH,, if formed with normal bonds, would have
only four electrons in the outer shell of the beryllium atom and would be electron deficient.
Periodicity and +Block This would make the molecule very unstable; that is why BeH, exists as a polymer. This is
Elements
an example of a cluster compound in which each atom shares its electrons with several
neighbours and receives a share in their electrons to acquire-a stabie configuration.
All the metals in the Mg-Ba series or their oxides react directly with carbon to give the
carbides (acetylides). MC,. These carbides are ionic in nature qnd hive a NaCl type of
structure (Fig. 5.2) with M?+ replacing Na' and C g 2 - replacifigcl-. Beryllium forms
methanide, Be,C, with carbon and acetylide, BeC,, with acetylene. Magnesium on
heating with carbon forms Mg,C, also, which is an allylide since with water it liberates
The carbides are named depending allylene (methylacetylene).
upon the hydrocarbon they liberate
on reaction with water. If it The alkaline earth metals bum in nitrogen and form nitriaes, M,N,. It requires a lot of
liberates acetylene. it will be named energy to convert the stable N, molecule into nitride ion, N3-, and this is recovered from
acetylide, and if methane is the very high lattice energies df the alkaline earth metal nitrides. The beryllium
liberated, it will be called as
'methanide'. etc.
compound is rather volatile while others are not. They are all colourless crystalline solids
CaC, + 2H,O + Ca(OH), + C,H, which k o m p o s e on heating and react with water to liberate ammonia and form either
acetylene the metal oxide or hydroxide, e.g.,
Be,C + 4H,O + 2Be(OH), + CH,
merhane 3Mg(s)+ ~ , ( g ) - ~ g f + ~ i - ( s )
Mg$, + 4H,O + 2Mg(OH), + ~ g : + ~ ; - ( s+)~ H ~ o ( I ) + ~ M ~ " ( o H - ) ~ ( ~2NH,(g)
)+
C'H,-C=CH
allyiene
Thermal Stability of Oxysalts
All the Group 2 elements form oxysalts. The thermal stability of the mysalts increases with
the increase in electropositivity of the metals. Thus, it increases down the group. The thermal
stabilities of the salts of Group 2 are less than those of the Group 1 meta1s:The

MCO, -
carbonates of alkaline earth metals are stable at room temperature. On heating, they
decompose into the corresponding oxides and carbon dioxide:
MO + CO,
The temperature at which the carbonates decompose are given as:
BeCO, < 400K ; MgCO,. XOOK ; CaCO,. 1200K ; SrCO,, 1550K; BaCO,, 1650K
The sulphates are more stable than the carbonates. On heating, they decompose into oxides
and sulphur trioxide.
MSO, >- MO + SO,
The order of decomposition temperature of the sulphates is:
BeSO,, 850K ; MgSO,, 1 150K; CaSO,, 1400K ; SrSO,, 1650K.
Alkali metal nitrates decompose into nitrites on heating whereas alkaline earth metal nitrates
decompose on heating to metal oxide, nitrogen dioxide and oxygen, e.g.,
2Ca(NO,), j 2Ca0 + 4N0, + 0,
SAQ 3
Explain inbrief why is the hydride bridge in (BeH,)" considered to be electron deficient but
not thebalide bridge in (BeCl,)".

5.3.3. Complexation Behaviour

Let us discuss another interesting property of these elements. i.e., their complexation
behaviour. Complex formation is favoured by small, highly charged cations with suitable
empty orbitals-of approximately the right energy with which the ligand orbitals can combine
(see Unit 4. Section 4.6).
Alkaline earth metals form more complexes as compared to alkali metals. ,The tendency to
form complexes (mostly with 0 & N donors) decreases with increasing atomic number.
Thus, of the heavier ions only Ca2+forms a comp!ex with ethanol. Beryllium having the
smallest ion in the group tends to form complexes most readily. It mostly forms complexes
with tetrahedral arrangement because of the available orbitals as shown below:
 Alkaline Earth Metals
No unpaired electrons so no
ground state covalenhbonds
Bc atom ~n Two unpaired electrons can
c x ~ ~ l estate
d form two covalent bonds

Be in [BeF4I2-
1
11 Two fluoride ions each donate
an electron pair into an
sp3 hybridisat~on empty orbital forming a
coordinate bond

The well hnown tetrafluoroberyllateshave a tetrahedral structure as shown in Fig. 5.6.

- - 2-
F

- F -
Fig. 5.6: ~&rafluorober~llate
complex ion. [BeF,I1 .
The arrows in the above figure indicate that two F ions form 'coordinate' bonds with
BeF,. However, once these are formed, aU the Be-F bonds tend to become similar.
Beryllium forms white crystalline molecular oxide-carboxylates, of which basic beryllium
Chelates are the ring compounds
acetate, viz., [OBe,(C%COO),] is typical and important for the purification of Be because formed as a result of coordination
of its volatility and solubility in organic solvents. Beryllium forms a number of chelates also ~~h ]&,ands having more than one
with ligands like oxalates, [Be(C20J2]2-(Fig. 5.7), and P - diketonate anions. binding sites.

Fig. 5.7: Beryllium oxalate complex ion, [Be(C,O,),I2-

In the hydrated salts, e.g., BeC0,.4H20 and BeS0,.4H20, beryllium ions exist in the form,
[Be(H20),]2+,where they show a coordination number of four.
Magnesium is known to form a very important complex occumng in nature, viz.,
chlorophyll; a green pigment of the plants which produces sugars for the plant in presence
of sunlight, CO, and H,O in a process called photosynthesis.
Chlorophyll
6C02 + 6 H 2 0 Sunlight
)C6H1206 +602
Glucose
Magnesium, in chlorophyll, is coordinated by four nitrogen atoms in the heterocyclic
porphyrin ring system (Fig. 5.8).
Periodicity and s-Block
Elements

Fig. 5.8: Skeleton of chlorophyll molecule

When water does not form lather

with it is
The rest of the elements from calcium to barium form comvlexes only with strong -
as hard water. complexation agents such as acety lacetone, ethylenediaminetetraacetic acid (EDTA), etc. In
Hardness of water is due to the
presence of heavy metal cations
fact, titrations are performed using EDTA in buffer solutions to estimate the amounts of Ca2+
like Ca2+,MgZ+and Fe2+etc. and Mg2+present in water, to determine the hardness of water.
SAQ 4
Why do alkaline earth metals form more complexes as compared to the alkali metals? Give
only two reasons.

5.4 ANOMALOUS NATURE OF BERYLLIUM - -- --

Beryllium, the first member of the group, appears to be quite different from the other
members, in the same way as lithium differs from the other alkali metals and for the same
reasons as discussed for lithium in the previous unit. Beryllium differs more from
magnesium than lithium does from sodium, in fact, the anomalous nature of the first
member of s- and p-block groups becomes more pronounced towards the middle of the
table. Also beryllium shows a diagonal resemblance to aluminium in the same way as
lithium does to magnesium. Also the properties in which beryllium differshorn magnesium.
it shares with aluminium in general. Let us now consider all the factors one by one.
a) The cohesive properties of beryllium are much greater than those of magnesium and
other elements in the group. As a result it is much harder and has higher melting and
boiling points.
b) It has smaller atomic radii, higher electron affinity and higher ionisation energy.
c) Its higher polarising power leads to all its compounds being largely covalent, with lower
melting and boiling points and enthalpies of formation (e.g., BeF,, m.p. 1073K, for rest
of the group about 1573K). All the compounds of Be are more soluble in organic
solvents than the corresponding magnesium compounds. They hydrolyse in water, and
in this respect they rather resemble aluminium.

5.5 SUMMARY
Let us now summarise the main points that we have discussed in this unit.
The general properties of the ~ r b u 6 elements
2 are similar due to the similarity in the
outer shell electronic configuration, i.e., ns2.
 Like Group 1 elcments. Group 2 elements also follow the group trends, i.e., increasing Alkaline Lrrth Metals
atomic size, density, electropositivity, reactivity. reducing power, hardness and
conductivity. Their ionisation energy decreases down the group.
The Group 2 metals are harder, have higher melting and boiling points, for~hydr2xidcs
which are weaker alkalies and form carbonates which are less stable than those of
corresponding
.. Group
. "
1 elements.
The complexation behaviour in the group is mainly restricted to beryllium and very few
complexes of the rest of the elements are known.
Beryllium being the first number of the group exhibits anomalous properties and shows
diagonal relationship with aluminium.

a5.6 TERMINAL QUESTIONS

1 The first ionisation energy of beryllium is greater than that of lithium. but the position is
reversed in the case of second ionisation energy. Why?
2 Why beryllium forms covalent compounds?
3 Describe the difference in the nature of bonding of BeH, and CaH,.
4 What are the usual coordination numbers for Be2+and Mg2+?What is the reason for the
difference?
5 Why do halidesand hydrides of beryllium polymerise?
6 Which is more stable to heat, beryllium carbonate or barium carbonate, and why?

ANSWERS
Self Assessment Questions

1 a) Since the effective nuclear charge felt by the outcr electrons in the atpms of Group 2
elements is comparatively higher, these elements are smaller in size than their
c~unterpartsof Group 1.
b) since Group 2 elements have two valence electrons, they have stronger metallic
bonding and show higher cohesive properties than their Group 1 neighbours. Thus
they are harder and have higher melting points as compared to the Group 1 elements.
2 If you subtract the lattice energies from the hydration energies ~f MCO,, you will find
the difference increasing from Mg to Ca, decreasing from Ca to Sr and again increasing
from Sr to Ba showing a decrease in solubility from Mg to Ca, an increase from Ca to Sr
and a decrease again from Sr to Ba. The maximum solubility is shown by MgCO,.
3 The hydrogen bridge in (BeH,),, is held together by one electron pair only and is electron
deficient in the sense that there is less than one electron pair for each pair of bonded
atoms. But in (BeCl,),,, each pair of bonded pair of atoms has the normal electron pair
and so, its bridge is not electron deficient.
4 As compared to the alkali metals, the alkaline earth metali form more complexes
because they are smaller in size and have higher cationic charge.
Terminal Questions
1 Because of its smaller atomic size and higher effective nuclear charge, the first
ionisation energy of Be is higher than that of Li. But the second ionisation energy of Be
is smaller than that of Li because of the stability of a closed shell configuration of Li+.
2 According to Fajan's rule, sm:.ll size and high charge density favours covalency and
therefore, Be has a strong tendency for covalency.
3 According to Fajan's rule, calcium forms ionic hydride while beryllium forms covalent
hydride.
4 The usual coordination numbers for Be2+and Mg2+are 4 and 6, respectively. The
difference is due to the very small size of Be2+and non-availability of d orbitals in it.
5 The monomeric molecules Be$ and BeCI, formed with normal bonds will result in only
four electrons in the outer shell of the beryllium atom making it electron deficient. By
polymerising, each atom shares its electrons with several neighbours and receives a
Periodicity and s-Block share in their electrons making the situation more favourable. Therefore, the halides and
Elements hydrides of Be polymerise.
6 BaCO, is more stable than BeCO,.
(Hint: Relate size of cation to size of anion.)

FURTHER READINGS
1 A NPW'Concise Inorganic Chemistry, J.D. Lee, ELBS, London, 3rd ed., 1977.
2 Chemistry: Facts, Patterns and Principles, W.R. Kneen, M.J.W. Rogers and P. Simpson,
ELBS, London, 4th ed., 1984.
3 Advanced Inor~[Link]. F.A. Cotton and G. Wilkinson, Wiley Eastern Ltd.,
New Delhi, 9th reprint, 1986.
4 Principles of Inorganic Chemistry, B.R. Puri and L.R. Sharma. Shoban La1 Nagin Chand
& Co., New Delhi, 19th ed., 1986.