2

CHAPTER

s-BLOCK ELEMENTS
Jentents belonging to groups 1(or IA) and 2 (or IIA) of the periodic table are called
1sblock elements. These have one or two electrons in their outermost s-orbitals. Group 1
are called alkali metals and have the
Nenents
hseconstitute six elements, namely; lithium general electronic configuration [noble gas] ns'.
potassium (K), rubidium (Rb),
(Cs) and francium (Fr). These are called allkali
N metals because they readily form oxides and
drovides which are alkaline.
The group 2elements of the periodic table are called alkaline earth metals and they consist
he elements beryllium (Be), magnesium (Mg), calcium (Ca), strontium (St), barium (Ba) and
atium(Ra). Their general electronic configuration is [noble gas] ns². These elements of Group 2
realso metals. The oxides of some of these mnetals were known much earlier than the metals
hemselves and these were called alkaline earth metals because these were alkaline in nature and
isted on the earth.
In this present unit, we will have a comparative study of the elements of these twO group
nd some of their salient features.
 -BLOCK ELEMENTS
ChemicalProperties
ermpar
gy tfromChara Thealkali metals exhibit high chemical reactivity. This is due to
() theirlow ionisation energies
eagnetnerigcy ihsepire\cetvuems.aN
ack to (ii) low heat of atomisation.
As the vaalue of ionisation energy decreases down the group from Li to Cs, therefe
eactivityof alkali metals increases from Li to Cs.
org and
The alkali metals are highly reactive towards the more electronegative elements such as
(halogens. Some of their characteristic chemical properties are given below:
Action with air. Allthe alkali metals get tarnished on exposure to air due to oftheoxifo
oxides at the surface. They burn vigorously in air or oxygen forming three types
of
(a)Normal oxides containing O² ion (oxide ion)
(b) Peroxides containing O,2- ion (peroxide ion)
(c) Superoxides containing O, ion (superoxide ion)the main product depends upon
When the metals are burned in a free supply of air, sodium forms peroxide, Na.
Li,0,),
Tithium forms only the oxide, Li,O (and some RbO, and CsO, respectively. No
notassium, rubidium and cesium form superoxides KO,,
oxide, sodium forms peroxides while o
amount of energ arises as to
superoxides.
why lithium forms only normal
size o
ons strike on the formation and stability of these oxides can be explained on the basis ofsmaler
ion strikes on t
The
metal ion) and the anion. It is known that smaller cation can stabilizeeffects.
(alkali This is the basis of lattice energy superoxi
eS, the electrons can stabilize larger anion.
larger cation
the peroxides contain 0, [or O O ion and
am has the lowe Oxides contain O- ion,
xtent. Theretor 0, [or O-.O ion.
to blue light ion and, therefore, has strong positive field around it.
Lithium ion is very small of lithium ion,t
in nature. Due small anion, O. In other words, because of smallsize
can stabilize onlya
towards another oxygen atom is prevented and, therefore, it cannc
duons readiy of negative charge Consequently, higher oxides are not formed. Sodium ion is lar
On-metals ofte another oxvgen atom.
field around sodium ion is weaker and does no
stabilize large anion. The positive
peroxide ion but it is strong enough to prevent furthe
-h are held upb conversion of
oxide ion into a
because of large size of K*,Rb* and Cs ions, the p
Superoxide ion.On the other hand,
-tal salts are ve
and allows the superoxide ion to be formed.
very weak
moleof acry These are briefly discussed
below :
A. Oxides
thermal decomposition of LiO, at 450°C.
Pure Li,O is prepared by 1
Li0, 450'C LiO +0,
theionsLan
pendsupont
2icsolids
havi prepared by the reaction of NaOH, Na,0, or NaNC
e so fattracti Sodium oxide, Na,Ois
metal.
Na,O, + 2Na 2Na,0
1
NaOH + Na Na,0+,H,
ese Imetal. ry stabilizeanother
veconversion
superoxide df an
negative
stabilize
0 descatlargieorn nai
re The Sodium PurOxides
e TheseA. weak Lithium [or contain metal The when
uneroxiaes.potaarissesiunmLi,thSuperoxides 1. exhibit
As()Propert
Chemi
alkThale i calies
ium () of vdes maalkTthalievity thei()
r
oxygen
large O--o] formation toforms Reroxides hal o ge
thn
esS
. omare
y O
andnormal Li,0 are and ion. of charge only rubidium the the Normal Ac of
tion lo w ELEMENTS
ion ion) why value
oxide, oxide can surface. with metals
al kali energies
isbrieflyallows Onanion.atom. O onlymetals containing theas ionisation heat lowmetalto
s
small
a is ion.
stabilize and lithium oxides O
eNa,O oxides prepared the ion towards very ion, and containing of of
and the
containing air. ionisation
ofaremetals
are Na,0 The the ar e their atomisation.
discussed Consequently,
theother into anion,small the stability
cesium burned
They All
highly
s of anion. torms oxide, increases
white, positive peroxideslarger the characteristic
is by
superoxidehand, a another vigorously
bum in high
otherNaNO,3Na + O". ion O, alkalireactive
tow energy
NaOH Na N,a +
+Na,02prepared thermal below peroxide It of only form Li,0 in O,ion chemical
heat K,O alkali because field In
and, anion. these
is aion from
Li,0, oxygenother
(and free(peroxide(oxide
normal (superoxide ion)ion metals decreases
and is i: on ion higher therefore, contain known superoxides
around oxides supply properties
chemical Li
lowish metals by
decomposition words, This ards to reactivity.
to of some tarnished get
se the 450°C
be
large
but oxidesatom that oxide, Cs.
it O, is can of ion) air
can reaction formed. sodium is has the down
is because smaller be Li,0,), KO, air, ion) oxygenor more
2Na,0 ’ ze prevented
sistrong are [orO basis peroxides
sodium
forms This
2Na,0+,N, th e
white, also ’ strong
not explained RbO, the
only of of ion sodium main electronegativeelements
on is
Rb,O be Li,O, of K*, of cation
of exposure grotup due
Na,+;
0 H, Lio";0,
NaOH, enough formed. small
is and,positive 0ion lattice and forming
aboveprepared Rb* product given
is 1 at weaker can on CsO, from
1 450°C. and totherefore, size forms
bright
500°C. Sodium energy
stabilize the three to
Na,O, prevent offield respectively. below
by Cs* and and basis depends air Li
lithium peroxide, to
yellowsimilar or ions, io n around ypes ofdue
does it superoxides effects. to Cs,
further cannot smaller sizeofothers while
form such
therefore,
NaNO, the is ion, upon the
and
reactions. notlarge it. Now
Na,Oy oxides
positive the
Therefore, t he formation
Cs,O with oidation prevent spreading
andattach
Theanioncationtheof
question metal. oxygen
containnormal while the
is field itwith and
oran sodium the can
 INORGA
APPROACHTO
MODERN
with F,.
whichis isoelectronic
peroxideionreaction of LiOH. H,Oand H,0,
and
B. Peroxides

Theperoxides
LË0.is
contain
prepared
industriallybythe
hyperperoxideby
slightly
O,

heating under
reduced pressure.
LIOOH.H,0 +H,0
dehrydraion o
subsequent LIOHH,O+H0,
2LiOOH HO
Heat
Li0, + H,0,+H,0
crystallinesolid which decornposes to
Lii0on heat
thermodyanamically stable white
Itis to Na,Oin alimitedsupply of dry oxygen (air) and the
above 195°C oxidizing Na
by yellowpowderof Na,O,.
Na,0,is prepared
togivepale
reactingthis further Heat
Na,0 Na,0,
Pale yellow

cannot be prepared by the above method because of he

metal peroxides prepared by the quantitative
The otheralkalisuperoxides, MO,. These are best
further oxidation to e (ammoniated)’ 0
oxidation s
metals in liquid NH e (ammoniated) 0.

C Superoxides only in the presence of large

paramagnetic O, ion, which is stable dissolvedlin cations
These containthe prepared byreaction of O, with sodium liquid
NH, ta
such as K Rb, Cs. Na0, is Na with O, at 450°C and 150 atm pressure. Other heavier alkai me
also be prepared by reacting by burning these elements in air.
superoxides can be obtained coloured paramagnetic powders by care
Sesquoxides, M.O, have also been obtainedcan as dark
decomposition of MO, (K, Rb, Cs). These also be prepared by oxidation ofliguid am
thermal are considered to be peroit
solutionsof the metals or by controlled oxidation of the peroxides. These
disuperoxides [M), (0,P (0,)J.
hydrolysis reactions.
The various types of oxides are distinguished by their
MO + H O ’ 2M + 20H
M0, +2H02M + 20H- +H,0,
2MO, +2H.0- ’2M+ 20H +H,0, +0,
The different types of oxides can be identified by these reactions.
2 Action with hydrogen. The alkali metals react with hydrogen to form hydrides which ae
ionic in nature (M"H).
2M +H, 2MH (M= Li, Na, K, Rb or Cs
Metal hydride
()The reactivity of alkali metals with hydrogen increases from Li to Cs.
(i) The ioniccharacter of the hydrides increases from Lito Cs. This is because of decrease in ionisation
energy down the group so that electrons become easily available to hydrogen for forming Hion
(iüi) The stability of hydrides decreases from Lito Cs. This is due to the fact that as thesize ofalkal
metal increases from Li to Cs, so that the M-H bond becomes weak. Therefore, the stability o
hydrides decreases.
(ip) The hydrides react with water, liberating hydrogen. Lithium hydride is used as a SOurceot

hydrogen for military purposes and for filling meteorological balloons.

LiH +H,0 LiOH +H, down
() The hydrides behave as strong reducing agents and nature increases
Pgroup.
their reducing
 g-BLOCK ELLEMENTS
3. Action with water. Alkali metals readily react with water to form hydroxides and hydroger
gasisevolved. As the electropositive character increases down the group, the reactivity with water
increaseson descending the group from Lito Cs,
2Li +2H,O 2LiOH + H,
2Na + 2H,0 2NaOH+ H,
2K +2H,O 2KOH+ H,
Lithium reacts somewhat slowly. But sodiun and the other nernbers of the family react s
rapidly with water that the hydrogen gas evolved immediately catches fire. Thus, alkali metals
cannotbe kept either in air or in water. They are norrmally kept in kerosene oil.
The hydroxides of alkali metals are strongly basic and the basic strength
The M OH bond in the hydroxides of alkali rmetals is very weakincreases down
and it can the ionise
easily group to
forn M and
OH- ions. This accounts for their basic
b
the bond
character. Since theionisation energy decreases
downthe group, between metal and oxygen becornes weak. Therefore, the and
basicsostrength
ofthe hydroxides increases accordingly. Thus, NaOH is a stronger base than LiOH on
etion of halogens. The alkali metals readily combine with halogens to form
ionic halides
MX.
2M + Xy 2MX
K= halogen)
2Na + CI, 2NaCi
The reactivity of halogen towards alkali metals increases on movíng down the
to decrease in ionisation energy or increase in electropositive character as we move down group. This is
the groun
Al the metal halides are ionic crystals. However, Lil is slightly
polarization (Lit being the smallest cation has maximum polarizing power covalent because of the
largestanion can be polarised to maximum extent). and iodide ion being
All the alkali metal halides except LiF are soluble in water. However, LiF is insoluble in
water
due to itshigh lattice energy because of small cation and small anion.
The alkali metal halides react with halogens and interhalogen compounds forming ionic
polyhalides.
KI + L, K[L;]
KBr + ICI K[BrICl]
KF + BrF3 K[BF]
5.Solutions in liquid ammonia. Alkali metals dissolve in liquid ammonia to give biue solutions
which are conducting in nature.
In solution the alkali metal atom readily loses the valence electron. Both the cation and the
electron combine with ammonia to form ammoniated cation and ammoniated electron.
M+ (x+ y) NH, [MNH)J le(NH),J
Ammoniated
Ammoniated
cation electron
The value of x and y depend upon the extent of solvation of the alkali metal ion and the
ron respectivety. The ammoniated electron is responsible for the blue colour of the solution.
The electrical conductivity is due to the ammoniated cation as well as ammoniated electron. Ihe
With increase n
te SOlutions are paramagnetic because of the presence of free electrons.
Oncentration, the paranmagnetic character decreases. This suggests that in concentrated soitaots,
he ammoniated electrons form electron pairs as :
2e (NH,y ’ Ammoniated
le(NH)J
electron pairs
electrons, these solutions behave as strong and
Due to the presence of the free or ammoniated solutions can reduce aerial oxygen to
valuable powerful and selective reducing agents.
Superoxide and peroxide ions without bond cleavage.
These

e (NH3y
e (NH3)y O, Peroxide ion
Oxvgen superoxide ion
 properties
many
ANOMALOUS
alkali
secondthirdenergy that
i)espects. ions(aq) : potential very hydrogen.
liberatingmetals Lithium tis hese electrons.
loseto 36
(i) ThoughTherefore, Li" The (ii)
ItThe of metalsstep).step)
(called (1)has
The However, high
AsLithium, It 6. On
These
reactalkali
theseAll can is
the is overall process we
value clear Reducing standing
size This lithium
BEHAVIOUR and The so the ionisation
have the be
metals lithium hydration with solutions
of the large smallest oxidation strongest easily from
Element
(E° the
um is net tendency Cesium
Potassium
Rubidium Sodium
Lithium
mainly belongs of learnt
of reaction: oxidation
=-3.04 first compounds Table nature. the
group is
effect that energy. metals oxidised. canMODERN
tom the Li(s) energy) size that element Table solutions
due to OF is it for M potential V). 2Na reducing 3. reduce
strongest compensates that and th e ionisation This
However, 2C,H,OH 2Li + are th at Alkali
and toLITHIUM 1.the (g) potential 3. APPROACH
owever, is + 2HCI 2M
containing
+ better Hence, alkali Standard 2NH, 2M+
slowly
its the alkali it change
is anomaly Acetylene of HC metals met al
hasreleased + is th e agent.
=
ioning hydrated nH,0M(8) M(s)
reducing greater M(s) the Mg) is group it reducing theymetals Cs Rb KOxidation L
Nareaction
depends may CH are liberate ions TO
is metals AND
it the property the is acidic
reduction
y differs in be property can the is have have strong INORGANIC to
group Li" higher the to thought strongest their
ns:DIAGONAL agent tendency maximum upon expected
be hydrogen agents very hydrogen
(ag) third -’ when explained hig h potentialsreducing
from energy +e
Cs K'+e Na'
+e unusually
(group because of th an strong +eRb +eLi
+ step. the values CHEMISTRY
the e to (aq) M M(g)M to(aq) +te M tM(g) heisolated reducingacetylide to
Sodium armine
Metal as
lose net proceed be 2C,H,OLi
NaC= 2MCI + H,+ atoms
such
hydrogen as of 2MNH,
aining
ATIONSHIP 1) occurs needed extent. (g) metal as: tendency of agents. :
The effect th e Oxidation
potential
(V)alkali low
and ofelectrons +e + CNa oxidation
its amount as
atoms agentleast (B.8c.
has greater easily Therefore, of goes e metals. Thi s oxidation
to three : + (E° = I,
remove Hydration Ionisation
energy
Sublimation potential lonisation
ener8yOxidation reducing
in as to 3.00 2.99 2.93 2,71 3.04 is H, +
bers most into indicated
H,H,
act Sem,
in ofsteps. the alcoholszero). potentials due
hydration
of solution energy the
gaseous as states. I1.
the large greater tot KUMD/GD
of electron Now, energy
solution agent Therefore,reducing their
energy by and and
the
racteristic released amount its
energy than state.
gOUp reduction due acetylene therefore
other
(n know we as agenh
M* to these
the (n of its
 97
ELEMENTS

) The polaristng pT of Li ion is quite high due to its small size which results in the covalent
Fitscopounds
S O aoznt dorbitals in its valence shell.
and the rest of family
se of the importantcharacteristics of distinction between lithium
are given below
a Lithium is the hardest of all the alkali metals.
of other elements
The melting and boiling points of lithium are much higher than those
not get tarnished readily
Lithium is less eactive as compared to other metals and it does
at
tforms only monoxide, Li.Owith oxygen while sodium forms peroxide, Na,0, and other
n)
MO,.
eements form superovide, ionic character than salts of other alkali metals.
This is
in) The salts of lithium have lower
Li ion.
eUe Of high polarizing power of forming nitride while other metals do not react.
() Itreadily reacts with nitrogen
6Li + N, ’ 2Li,N
combines with carbon and silicon forming the carbide and the silicide.
() Onlv ithium while the
Lithium hydroxide and carbonate are unstable and decompose on heating
(pn)
compounds of the rest of the family members are stable and do not decompose:
Qresponding 2LiOH Li0 + H,0
LiCO, Li,0+CÔ,
(ix) Upon heating, lithium nitrate gives nitrogen dioxide and oxygen.
Heat
4LINO,
2Li,0 + 4NO,
Nitrogen dioxide
strong heating form corresponding nitrites and
Sodium nitrate and potassium nitrate upon
evolve oxygen. Heat
2NaNO, 2NaNO, +O,
(LiH) is more stable as compared to the hydrides of othermembers
() The hydride of lithium
of the family. while the salts of sodiumare insoluble
and nitrate are soluble in alcohol,
(a1) Lithium chloride
in alcohol.
hydroxides of other metals.
(1) Lithium hydroxide is much less basic than the soluble in water. The
(i) Lithium fluoride, carbonate, hydroxide, oxalate are sparingly
COTresponding salts of sodium and potassium are readily soluble.
hydrated than those of sodium.
() The Li ion and its compounds are more heavily
However, lithium shows diagonal relationship with magnesium.
DIAGONAL RELATIONSHIP
similarities with the elements
t nas been observed that some elements of second period show
period present diagonally toeach other. though belonging todifferent groups. 1his 1S khow
as diagonal relationship. Thus, the elements present diagonally is called
similarity in properties of
diagonal relationship. This is shown below :
Second period Li Be B
 TO INORG
COMPARATIVE STUDY OFAPPROACH
MODERN GENERAL CHARACTERISTICS OF GROUP 2 ELEMENT\
40
alkaline earth metals are given in
of
important physical constants
discussed below alkaline earth metals
The are
characteristics Physical constants of
general physical Table 4
Ca ha
Be Mg
12 20
Atomicnumber 4008 87 62 137.34
24.31
910 197 215 222
Atomicmass 12 160
Atomic radius (m) 100 118
27 72
lonic radius (pm) 1.05 203 362
1.85 L74
Density (g cm)
lonization enengy S03
738
|146 1064 965 9
1757 1451
14S49 4910
1.31 1.00 098 0.89
1,57
Elextronegativity
Oidation state
1041 1000
Melting point (K) 1500
l64 2123
2770 1378
Boiling point () 290
-1.70 2.37 287

Physical Properties
1. Atomic and ionic adii. The atomic and ionie radiùof the members ot the tamiy
than the corresponding memters ot the alkali metas The alkaine earth netalsAsa havea hgthet
rsult
charge andtherefore, theelectrons are attractead more towands the nucleus thera°ià
and ionic radi are smallerthanthose of alkali metals C moving ddown the group.
due to gradual increase in the nunmber of the shells and the screning ettt densedha
2. Density. Alkaline earth metals have low densities but are eatvelv moe
alka
metals This is becausetheir atomie sizes are smaller than the coreNdS considera
decreases on moving down the ghoup upto calcium but it theni s e s
tadium
3. Melting and boiling points. Alkaline vrth netas have ow melting
wich are higher than the corresponding alkali metas in the sae
saller siee However, elting and boiling oints do not shor gulartreNs
lue carth metals have smaller sae as comyand to alkai hetalk Tlherews they
packed in their crystal latticesad hence they have higher eltinganN i s
onizatin eeges
4 lonization energy, The alkaline earth etals
have lor
large sze of the atums Sice the atomi siae Ceases down the gro a n sf
decreases (lable 3) Acoyarison of theionisatiot the
shows that the meabes present in thesnd gro enegies
have higher valuesas
IOup Ibexause they have saller s ai
the atos elkvtrons
are oe
Aigber
lLnay be otedthat althouxhl ,values of alkaie rth ealsdve
etals, the l, alcs of alkaline ourth ehas uty A eal)
energy values of sodium (alkali eta) ad sY ewrth
agnestunt (alkabie
 41

Element IE IE
Na 496 kJ moi1 4564 kj mo!
738 k] mol! 1451 k] mol
Mg
from a cation which has
alkali metals (ie., Na) the second electron is to be rernoved
CSeof hand, in the alkaline earth metals (ie.,
aire a noble gas configuration. On the other
:(1s°25°2p3s') which still
Mg
i electron is to be removed from a monovalent cation,
Mg can be rernoved easily.
eund
he
eetroninthe outermost shell. Thus, the second
electron in
1E Na(g)
Nal g) Na(g)
1s22p
1s223s! 1s2s2p
Stable configuration
Mg(g)
Mgl g) Mg(g)
1s2s2p3s! 1s922
1223s?
Not very stable
gas
because the electron is to be removed from stable noble
The E, of Mg will be very high
alkaline
character. Because of the low ionisation energijes of
EEectropositive and metallicelectropositive in nature. However, these are not as strongly
Enetals, they are strongly because of comnparativeyhigher ionisation energies.
group 1
positive as the alkali metals of down the group ie. from Be to Ba.
Bietupositive character inreases Mg, the alkaline earth metal salts impart
Be and
íCharacteristic flame colouration. Except for
erisiccolours to the flame.
Flame colour
Metal
Beryllium
Magnesium
Brick red
Calcium
Crimson red
Strontium
Barium
Grassy green
Blue
Radiumn
characteristic flame colours.
Beryllium and magnesium do not give any colours because their ionisation energies
characteristic flame
The earth metals give excited to higher energy
alkaline the valence electrons in
these atoms can be easily
electrons (excited state is
Therefore,
the energy of flame of bunsen burner.
When these excited
radiations which fall in the visible region.
Wobzo)e state) Come back to grOund
state they emit
hand, beryllium and magnesium atoms
are

iBieschkre, hey give colours to the

flame. On the other
are very high. Hence, the energy of the flame

ztaratufivfcolour
eiclyient
Smaller and their íonisation
to excite their electrons
in Bunsen flame.
energies
to higher energy levels. These elements, therefore, do not

alkalineearth metals exhibit a valerncy of +2 as

they
 42 MODERN APPROACH TO INORGANIC CHEMISTRYy
(B,86. 1, Bem. 1, KAUM
energy (lE,) of alkaline earth metals is greaterthan the first
that if ionisation energy is the only factor involved in theionisation energy (E). It, hus
formation
expect that alkaline earth metals would prefer to form +1 ions(M' )
of divalent
they predominately show +2 valency, eg, Mg",Ca, Ba' etc. rather than 42ions(M"), ons, weap eawos
This can be explained as : Ahu
() Divalent ions have the stable noble gas configuration.
(i) In solution, the +2 ions of alkaline carth metals
hydration energies of M²' ions makethem mnore stable than are extensively hydrated
M' ions. Itis
of energy released when M2 ion is dissolved in water is
much more than thatandhe the hi,
observed
amount of extra energy released in the hydration of +2 ions is
more than that for M' ion. arnou
energy required for the formation of such ions, compensates the second This lary
(ii) In the solid state, the divalent
cations form stronger lattices than monovalent
therefore, alot of energy called lattice energy is released. It is the greater lattice
ionisatu
compensates for the high second ionisation energy and
Mion.
cations
is responsible for its greater energy of Mion uhid
and
stability as
This can be easily understood by
compared y
of MgCland MgCl, in water. The considering the overall energy changes for the formatign
various steps are:
Mg(s) Mg(g)
Mg( g) AHublimation =150 kJ mo-1
Mgt(g) +c AH =737 k] mol-1
VACI,(s) CI(3) AH,"atomisation = 122 kJ mol-1
CI(g) C(g)
Mg'(g) + CH(g)+ntH,0 ’ Mg'(aq) +CI(aq) AHEA. =-348 k< mol-1

Mglo)
Net energy change= -74 kJ mol-1
Mg( g)
AHydration = 150 kJ mol-1

Mg( g) Mg2 + 2e AH,sublimation =150 kj mo-l

Clh( 3) ’ 2C1 AHg =2188 k] mol-!
2C1+ 2e ’2CI AH,atomisation =2 x 122 k< mo
Mg?(g) +2CI(g) +nH,0’ Mg'(aq) +
2CI(a9)
AHE.A.
AH
=2x348 k] mol
Net energy change =-785 k] =-2670 kJ mol
Thus, it is clear that during the mol-1
therefore, it is more readily formed. formation MgCl, in water, more
of
Chemical Properties energy
is released and

Because of their low ionization energies and

metals have strong tendency to lose valence high electropositive
of these elements increases on going down the electrons.
Therefore,
they are
character, the alkaline earth
less reactive than alkali metals. The
chemistry group, However, alkalinevery
is mainly
reactive. The reactivity
earth
(M). Some of the general trends are discussed below dominated dipositive
by the metals are, in general,
1. Action with air or oxidation state
oxygen-Formation
electropositive than alkali metals,
of
react with air or Oxides. The alkaline earth
However, Ba and Ra form peroxides. oxygen slowly upon heating to metals being less
form Oxides, M0.
2M +O, Heat
’ 2MO
(M = Be, Mg or
Monoxide Ca)
2M +O, Heat
MO, (M= Ba
Peroxide
or Sr)
 BLOCK ELEMENTS
43
The reactivity with oxygen increases as we move down the group due to increasing electropositive
Tacter of elements.
the
The monoxides can also be prepared by decomposition of their carbonates :
MCO,
Carbonate
CO, (M= Be, Mg, Ca, Sr or Ba)
MO +

Monoxide
Amongthe oxides, BeOis amphoteric while oxides of other elements are basic in nature.
BeO
Amphoteric
MgO CaO,SrO, BaO
Weakly basic Basic
The amphoteric character of BeO is supported by the fact that it reacts with acids as
well as
kalies.
BeO + HCI
BeO + NaOH
BeCl, +H,0 (Basic nature)
Na,BeO, +H,0 (Acidicnature)
Sodium beryllate
The increase in basic character of oxides from Be to Ba is because of decrease in polarizing power
witn
iLCreASe in ionic size.
The oxides of Be and Mg (BeO, MgO) are almost insoluble in water while the oxides of rest of
he metals dissolve in water to form hydroxides.
CaO +H,O Ca(OH), + Heat
The insolubility of BeO and Mg in water is due to their large lattice energies.
2. Combination with hydrogen-Formation of hydrides. All the elements except beryllium
umbine with hydrogen upon heating to form ionic hydrides, MH,.
Ca + H, Heat
CaH,
Calcium hydride
Beti,, however, can be prepared by the reaction of BeCl, with LiAlH,
2BeCl, + LiAIH, 2BelH, +LiCl + AlCI,
Beli, and MgH, are covalent while allother hydrides are ionic. Calcium hydride is known as
hy£rolith. The hydrides are highly reactive with water and form hydroxides and liberate hydro
gen.
CaH, + 2H,0 Ca(OH), + 2H,
3. Action with water--Formation of hydroxides. The alkaline earth metals have lesser
adency to react with water as compared to alkali metals. They combine with water slowly to form
hydroxides.
Ca + 2H,0 Heat
Ca(OH), +H,
Magnesium does not react with cold water but it decomposes hot water.
Mg+ 2H,O ’ Mg(OH), + H,
hot

Mg + H,0 ’ MgO + H,
Like alkali metals, the hydroxides are basic in nature and basic strength increases down the family.
Ihe basiccharacter of hydroxides is due to the low ionisation energies of these metals
DRcause
UH of low ionisation energies the M-O bond in MOH is weak and it can cleave to give
iengtonsh of n solution. Since, the ionisation energy decreases
Be(OH), is
down the family, therefore, the basic
samphoteric, Mg(OH), is
the hydroxides increases. For example,
while other are strong bases. mildly basic
 INORGA Sem. 1, KUMOU
APPROACH TO
MODERN bastcthay
metals are less carth
alkali metals of the
The udrorides
basic
of alkaline
strength of
The lesser ionizationenergies
()high
smallionicsize,
and
earth
hydroxidesof
alkaline metal hydroxides is
Cor esponding
due their
to

()Asadipositioe
result,the M on
charge theions.
Obond inthesehydroxidesiss relatively stronger than that ot coresp
(ii)
break. Therefore, they are less basic than

Cmetor esapl.omding
therefore, does not
alkali metals and less:soluble than alkali
metals.
of alkaline earth metalsare metal hydroxides
increases with increase in size of the Ho
The hydroxides in water
hydroxides
the solubility of insoluble, Ca(OH),is sparingly
soluble while Sr(OH), and BelO
soluble. are almost
Mg(OH),This
lattice energies
Ba
trendis due toincrease in size of the cation on moving down the group so tha
decrease. Due to
decrease in lattice energies, the hydration
hydroxide in water increases.
(O H\ ,e
energjes betome
solubility of
and thewith nitrogen. The alkaline earth metalsreact with nitrogen to form nitrides,
4. Action 11
and more
liberate nitrogen.
which react with water to
3 Ca + N, Ca,N,
Ca,N, +6 H,0 3Ca (OH), +2NH,
Be,N, is volatile whereas other nitrides are not volatile.
5. Formation of halides. All the alkaline earth metals combine with halogens s* % B
temperatures forming their halides.
M+X, ’ MX, (X= CI, Br)
The metal halides can also be obtained by the action of halogen acids on metals, their
carbonates and hydroxides.
MO + 2HX ’ MX, + H,0
M(OH), + 2HX ’ MX, + 2H,0
Anhydrous beryllium halides cannot be obtained from materials prepared in aqueus
tion because of the formation of hydrated ion [Be(H,0),12+ (e.g. [Be(H,0)|Cl,). The dehydr
these products result in hydrolysis.
Heat
[Be(H,0),]Cl, Be(OH), + 2HCI lethas
The anhydrous beryllium fluoride and chloride can be prepared by the following
BeO +2NH,F ’ (NH),[BeF ]
Heat
BeF, +2NHF
BeO +C+ Cl, 600°C-800°C
BeCl, +CO
800°C
2Be) +CC, 2BeCl, +CO, iodue
and
Among alkaline earth metal halides, except the chlorides, bromides insized
alkaline earth metals are fairly beryllium,
Their ionic character increases with increase
cation as we go down the group.ionic.The
COvalentbecau
small size and high charge of Be beryllium halides, on the other hand, are lowermeltig
ion. Being covalent, beryllium halides have areonlyspurt
boiling points than other alkaline earth
soluble in water, but they are freely metal chlorides. The berylliunmsolvents.halides
stal
soluble
Beryllium chloride has interesting in ether and other organic In
sold
puil
has polymeric chain structure in solid state and Vapour state.electron
chlorine atoms which structure as shown in Fig. 1. The chain of free thiscase
form arises because In by
beryllium
Cl atoms.
atom is intermolecular coordinative
considered to be sp' hybridised covalent bonds.Surrounded

and is tetrahedrally
 BLOCKELEMENTS :0:
45

Be :0:
Be
Be

CI

Be 98 Be Be

Fig. 1. Structure of BeCl, in the solid state.

adjacernt tetrahedral planes are at 90° to each other and CIBeCI bond angle is 98° instead of
The
normal109.28 angle of a regular tetrahedron. The smaller angle gives stability to the structure
hecauseitlessens the repulsive interactions between neighbouring Be atoms in the chain by keeping
hem further apart.
In the vapour phase BeCl, tends to form chlorobridged dimer (Fig. 2) which dissociates into
state, the linear
inear monomer (Fig. 3) at high temperatures of the order of 925°C. In the vapour
RCI, molecule involves sp hybridisation of beryllium.

CI-Be Be--CI C Be-CI

Monomer
CI
Dimer

Fig. 2. Chlorobridged dimer of BeCl,. Fig. 3. Linear BeCl, molecule.

fluorite type structure.
Most of anhydrous halides of alkaline earth metals have
weak ligands such as Et,O, (CH),CO,
Beryllium chloride chain structure may be broken byBeC1, L, (where L is a ligand) as well as
CHNO, to form four coordinated molecular complexes as [BeL, [CLð. Ih these complexes
Py,etc. to form ionic complexes as
by strong ligands like H0, NH, tetrahedral arrangement of ligands.
beryllium is sp° hybridised with
AND MAGNESIUM AND DIAGONAL
ANOMALOUS BEHAVIOUR OF BERYLLIUM
RELATIONSHIP family show anomalous behaviour as
member of the alkaline earth metals
Beryllium, the first members, However, beryllium shows
diagonal
magnesium and the rest of the
COmpared to
Telationship with aluminium.
following reasons
It is mainly because of the
() small síze of the atom or its ion
electronegativity
() highionisation energy and
(ii) absence of d-orbitals. and magnesium are given below :
differences between beryllium
Some of the important
magnesium.
() Beryllium is harder than melting points as compared to magnesium.
() Itpossesses higher boiling and On the other hand
water even at elevated temperatures,
(ii) Beryllium does not react with
magnesium reacts with boiling water.
Mg + 2H,O ’ Mg(OH), + H,
magnesium does
Beryllium does not combine directly to fornm hydride whereas
(iv)
 MODERN APPROACH TO INORGANIC
48
CHEMISTRY (B.Sc. I, Serm. ,
In case of alkaline earth metal hydrides, BelH, is covalent while
due to theMgH, is
hydrides of calcium, strontium and barium are largely ionic due KUMDU
partly JGDU
character of the metals. greater ionic. Th
The alkaline carth metal hydrides are reducing
hydrogen. agents and are hydrolysed by water li electroposits
MgH, +2H,0 Mg(OH), +2H,
CaH, +2H,0 Ca(OH), +2H,
Therefore, they also act as reducing agents.
BeH, and MgH, are examples of polymeric solids.
structure as shown in Fig.4. Beryllium is bonded to four (BeH,), polymeric has very interestire
two bonds. The bond between two hydrogen atoms and hydrogen is formi
beryllium atoms and one hydrogen atom is a special type c
bond known as three centre electron pair bond (also called banana bond). It covers three
Conta atoms and

Be Be
Besb Be

Fig. 4. Structure of polymeric BeH,.

CaH,, BaH, and SrH, are ionic solids (M² and H).
arrangement. These have slightly distorted hcp
 INORGA
APPROACH TO
MODERN
56

CONGEPTUAI
uestions
Q.1. BeCl, gives
an acidic solution when dissolved in water.
forming H' ions
Why?
(M.D. U. 2018, 24
and therefore,the solution is acidic.
hydrolysed in water
Ans. BeCl, gets 2H,0 - Be(OH), + 2H' + 2CI
BeCl, (s) + Explain.
metals are colourless and diamagnetic.
earth
Q. 2. Salts of alkaline their salts. These dipositive ions have
Ans. Alkaline earth metals form dipositive ions in
electrons. Therefore, these compounds are noble
g
colourles.
configurations with no unpaired
diamagnetic.
Q.3. Lil, is less stable than Csl,. lattice. Thet
This is due to lattice energy effects. The large cation stabilizes a large anion in its
Ans. l 10n.d nd s
CsI, is more stable because Cst being large cation can stabilize large
Q.4. Give one word (yes or no) to the following :
?asht
(i) Is magnesium likely to be stronger reducing agent than strontium
G) ls the size ofSP* ion more than that of Ca ion ? t eo st ointennud
(ii) Is Mg (OH), stronger base than Ca(OH), ?
(iv) Is barium likely to be metallic ? oldenocebidd
Ans. () No () No (i) No (iv) Yes
Q. 5. Why are alkali metals soft and have low melting points ?
Ans. Alkalimetals have only one valence electron per metal atom. As a result, the binding energy of alkali
metal ions in the close-packed metal lattices are weak. Therefore these are soft and have low melting
points.
0. 6. Describe the difference in structure between CaH, and BeH..
Ans. CaH, is an ionic solid consisting of Ca and Hions having slightly distorted hcp arrangement. On
the other hand, BeH, has polymeric bridged like structure (BeH,),.

Be Be

0.7. LiF is insoluble in water whereas other alkali

metal fluorides are soluble.
Ans. Both Lit and F ions have small size and
energy of LiF is also high but, it istherefore, LiF has high lattice energy. Although the
less than lattice energy hydratiot
-1034 kJ, lattice energy =-1045 kJ). Therefore, it is insoluble. (hydration energy of Lr
On the other hand, all other alkali metal
tluorides have lower lattice energies than
hydration energies and therefore, are soluble. correspond
Og When burnt in air, lithium forms
normal oxide, Na the peroxide and K the
Ans. Li' is very small in size and has strong field around it. It can superoxide.
and therefore, forms only Li,0. It cannot stabilize other large stabilize only small sized oxide O2- ion
superoxide O,). anions such as peroxide (0, and
Nat being larger in size can stabilize large peroxide ion O, and
K* being large can also stabilize large superoxide ion O, therefore forms peroxides.
forrming superoxides.
 ELEMENTS
67
LiH,LIFand Li,N show
exceptional thermal stabilities.
AnsLi's emmall in size and has exceptionally high charge radius ratio. Therefore, its salts with small
Explain.
anionssuch as ,H
andN are exceptionally
stable due to high lattice enerzies.
Which out of Li or Na has
greater value for the following their :
() Hydration energy properties
i) Stabilityof hydride
ii) Stabilityof carbonate
(iv) Basic character of hydroxide
io) lonisation energy.
(ii) Li (ii) Na
Ans. () Li (iv) Na (v) Li
Q11. Which out of the following and why can be used to store an alkali mnetal ?

H,0, C,H,0H, Benzene

Ans. Bernzene can be used to store an alkali metal because other substances react with alkali metals as
Na + H,0 NaOH +AH,
Na +C,H,OH CH,ONa +AH,
n12. Mg'* is much more hydrated than Na. Why?
Ans. The extent of hydration depends upon the charge density (charge/size). Mg? ion is smaller in size
than Na' and has twice the charge than Na. Therefore, its charge density is high and hence is
extensively hydrated.
0.13. Carn sodide ion exist ?
Na in ethylamine.
Ans. Sodide ion, Na exists in cryptates. Sodium forms the compound [Na(2,2,2-crypt)] ligand shields the Na
This is a golden yellow solid which is diamagnetic. In this, the large cryptate
ion.
ion and does not allow it to combine with Na
shuttles and submarines ?
Q. 14. Why is potassium dioxide used in space carbon
and submarines because it absorbs the exhaled
Ans. Potassium dioxide is used in space shuttles
dioxide and excess moisture and releases oxygen gas.
4KO,(-) +2C0,g) K,CO,s) +30, (g)
2KHCO,(s)
K,CO, (3) + CO,(g) +H,o (Pb. U. 2014)
hydride in water ?
V15. Can youdissolve sodium because it gets hydrolysed with brisk evolution
of
cannot be dissolved in water
Ans. No, sodium hvdride
hydrogen gas.
NaH + H,0 ’ H, + NaOH
0.16. Answer the following :
with water ?
Which out of Li, Na or Cs reacts violently
() complexation ?
alkali metal exhibits the tendency to
(i) Which
hydrated : Nat or Mg'* ?
() Which one is more metals, which element mainly
forms covalent compounds ?
alkaline earth (M.D.U. 2018)
(iv) Amongst the CaC0, gives flame colouration ?
MgCO, or
(0) Which of the two
Ans, (i) Cs
(ii) Li
(ii) Mg2+
(iv) Be
(o) CaCO,
 MODERN APPROACHTOINORGANIC CHEMISTRY (B.Sc. I, Sem. I, KU.MDUC

58 or not ? solublein water

soluble in water disodium salt is carbonates a
Q. 17. Is
Ans. EDTA
EDTA
is not soluble
islithium
in
carbonate
its
water but
unstable
0. 18. Why carbonate, Li,CO, is unstable
while other alkali
because its
metal
relatively stabj
constituent ion, Lit issmall and
stabilise the big carbonate ion and
Ans. Lithium small Lit ion cannot
in size. The
unstable and
decomposes
effectively
to LiO having
small Lit and O ions. therefore,
Li,0 + CO, can stabilise the
Li,CO, metal ions being large in size Co i
alkali
On the other hand, other
effectively.
BaCI, will be more hydrated?
Q. 19. Which of the two: MgCl, or
because Mg* ion is smaller in sizeh .
hydrated than BaCl,. This is can be more easily b
Ans. MgCl, will be more ion is large. As a result, it
therefore, charge per unit area on Mg+ in ethanol ?
stored in kerosene oil and not
Q. 20. Why are alkali metals these metals do not react with kor
are stored in kerosene oil because
Ans. Alkali metals and therefore, cannot h
hydrocarbon). However, alkali metals react readily with ethanol
in ethanol.
2C,H;OH + 2Na’ 2C,H,0ONa + H,
Q. 21. Which out of two : Mg(OH), or Ca(0H), is stronger base ? (Pb..
Ans. Ca(OH),
Q. 22. How can you stabilize a sodide, Na ion ?
Ans. Sodide ion, Na can be stabilized by complexing with a cryptate.
Q. 23. Out of MgC0, and CaCO,, which will give flame colouration ? M.D.U
Ans. CaCO,

Multiple Choice Questions

OHSEGTAN:XQuestions
Choose the correct answer from
1. The alkali various alternatives given:
metal peroxides are white
(a) 2 ionic solids and
(c) 0
contain the anion :
(b) O,
2.
Chlorophyl
(a) Be helps in
photosynthesis (d) O.
process. Which metal is present in
(c) K
3. The
peroxides of alkali
(b) Mg
(d) Li.
chloropny
(a) O metals contain an ion
which is
(c) N,
4. The order of (b) O isoelectronic with
(a) Cs > Rb> K> reactivity
of
Na > alkali metals with
(a) E,
ALOCKELEMENTS
59
7 The covalent character of alkali metal halides increases as (for sarne alkali metal) :
(a) <Br <CI<F
(c) Br<I<CH<F (b) F< CH< Br <t
geometry of (d) F<CH<t<Br.
8. The
(0) Tetrahedral
beryllium oxalate complex ion is :
(c) Octahedral (b) Linear
9. Lithium alkyls react with CO, to give: (d) Square planar.
(a) Carboxylicacids
(c) Alcohols (b) Ketones
(d) Esters.
Which of the following statements is not correct ?
i) In alkali metals group, electropositive character
increases frorn Li to Cs
(b) BeCl, is linear molecule in vapour state but it is
polymnericin solid state
(c) The hydroxides of alkaline earth metals are more basic than alkali metal
hydroxides
( Alkali metal hydrides are reducing agents.
11. Sodium burns inin excess of air to form :
(a) Na,O (6) Na,O,
(c) NaO, (d) None of these.
12. In basic beryllium acetate, berylium atoms are present :
(a) at the corners of tetrahedron
(b) along the edges of tetrahedron
(c) at the centre of tetrahedron
(d) at the centre and at the corners of the tetrahedron.
13. In the solid state, the structure of beryllium chloride is :
(a) bridged dimer (b) polymeric chain structure
(c) linear (d) tetrahedral.
14. Which of the following ion has maximum ionic mobility in aqueous solution ?
(a) Nat (b) Lit
(c) Rbt (a) K*.
15. Which of the following ion has highest enthalpy of hydration?
(a) Rbt (b) Cst
(c) Nat (d) Lit.

TAnswers toObjective Questions

1. (c) 2. (b) 3. (d) 4. (a) 5. (c) 6. (2) 7. ()
9. (a) 10. (c) 11. (b) 12. (a) 13. (b) 14. (c) 15. (d).