SBLOCK ELEMENTS

Some Key points about the Chapter

Group IA Group IIA
Alkali metal ( ) Alkaline carth metal (11 ysi a)
Li Be
Na Mg
K Ca
Rb Sr
Cs Ba
Fr Ra
Alkali metals
" General outermost electronic configsration (}IR freU) ’ns
(i) lonisation enthalpy increases. Li (i) atomic radius and ionic radius
(i) melting point and boiling point Na increases.
increases K (ii) density increases.
(ii) degree of hydration of the Rb (ii) eleçtropositively increases
cations and hydration enthalpy Cs (iv) basic character of metallic Oxide
increases. Fr. increases.
"Radius of the hydrated ions (cations) increases in the following order -’ (AIS RA)
[Li(ag)]* > [Na(aq)]* >[K(a)]*> (Rb(aq)]' >[Cs(aq)]*
" lonic mobility (aa AbO) increases from (Li(aq)]' to [Cs(aq)1*
" Istionisation enthaply of thealkali metals is low but 2nd ionisation enthalpy is very large as
M ion acquires insert gas configuration.
" Due to low ionisation energy alkalimetal shows (except Li) photoelectric effect ( y
Te1). Cs is used in photoelectriccell.
" Alkali metals and salts of alkali metal give flame test.
Li-Crimson red, Na - golden yellow
K- Violet, Rb- red violet, Cs blue violet
S119 fd) (M/Mt)
The order of standard oxidation potential (
Li> Cs > Rb> K> Na
the strongest reducing agent among he alkali metals. The heat of sublimation
Li is hydration eneroy
(DfoHgf)and ionisation enthalpy of Li is large but due to high
agent.
of Li" (g), it becomes strong reducing
Alkali metals are soft. They have one valence electron, so the metallic bond is very weak.
They have low melting point and boiling point due to weak metallic bond and low
cohesive energy (9fà)between the metallic atoms present in the crystal lattice (Gt
aTG).
They are paramagnetic and their cations are diamagnetic in nature.
When exposed to air they form oxides, hydroxides, carbonates at the surface due to
reaction with O,, H,0g) and CO,.
"Li forms monooxide (Li,0), Na forms Na,0 and Na,O, and K, Rb, Cs form superoxides
(KO,, RbO, CsO,). Due to smaller size, Lit can not stabilize larger anion 0 or 0;.
pure oxides and peroxides are colourless and diamagnetic, but superoxides are
coloured and paramagnetic.
Alkali metals react with H,0 to form metal hydroxide and H, Reactivity increases from
Lito Cs.
2M + 2H,0 ’ 2MOH + H,
.Heat af formation (oda B) of the metallic halides of alkali metals is negative.
(AH°=-ve) The order of AH°, for fluorides
LiF> NaF > KF> RbF> CSF
LiF is most stable and CsF is least stable.
" Melting point of alkali metal halide for a given halogen follow the order
Li< Na> K> Rb >Cs NaCl >KCl> RbCl >CsCl > LiCl (melting point) ( G ) (this
is due to increase of lattice energy from CsCl to NaCl)
Melting point of LiCl is lower than NaCl. This is due to high polarising power of Li ion (¢Li)
Covalent character of LiCi is more than NaCl.
NaF > NaCl> NaBr > Na (melting point)
LiF <NaF < KF <RbF <CSF(Solubility) (JO)
this is due to high lattice energy, LiF is water insoluble.
" CsI is water insoluable due to lesser hydration energy of I ion.
( a ) in nature. They
" Alkali metal hydroxides are white crystaline and deliquescnt
to CsOH. Thermal stability
are highly water soluble. Solubility increases from to LiOH
increases from LiOH to CsOH.
Basic strength (#1O 1) of metal hydroxide increases from LiOH to CsOH.
-H.1
Solid hydrogen fluorides KHF, and NaHE,2 are stable which contains [F
1on.

" Li only forms nitride (Li,N)

LuNO, and Li,CO, undergo thermal decomposition (v| fAAG) due to large polaris1ng
power of Li,N-0 or C- 0bond becomes weak.
O=c0°Li O*N-0Li" Li,co, Li,0 +C0,
\oLi 4LiNO,=2Li,0 +4NO, +0,
 The sodium and potassium together constitute sodium pump which is also known Nat
K* pump.
. Compounds of Na:
() NaOH is prepared by (a) Soda lime process (b) Hg-Cathode cell
Soda lime process:-Ca(OH)2 + Na,CO3 = CaCO3 + 2NaOH
Hg-Cathode cell:- During electrolysis of brine solution Na is discharged at Hg cathode
toform Na, Hg
(Na amalgam) Nat + e = Na
Na + Hg=Na, Hg
then Na, Hgreacts with water to form NaOH
1
Na, Hg + H,0 ’ NaOH + Hg+;H,
[due to overvoltage Hisnot discharged at Hg cathode]
(ii) Microsmic salt:- It is prepared by the reaction of NH,Cl and Na,HPO, in 1:1molar
ratio and dissolved in hot water and cooled.
NH,CI+Na,HPO, = Na (NH,) HPO, +NaCl.
On heating Na(NH,) HPO,, NaPO, is produced which produces coloured beads of ortho
phosphate with oxides of transitional metals
NaPO, +CuO = CuNaPO, (blue bead)
(iü) Na,O,:- 2Na + O,’ Na,O,
-1
2Na + 0, ’ Na,0
Na,O, is a strong oxidising agent
+2 +6
Mn(OH), + 2Na,O, = Na,MnO4 +2NaOH
C is oxidised into Cro, by Na,O, in alkaline medium.
Na,O, +2H,0 = 2NaOH +H0,
2Cr + 3H,0, + 10OH = 2CrO, + 8H,0
Na,0, isused to purify air
Na,O, + CO = Na,CO,
2Na,O,+ 2C0, =2Na,CO, +0, 500°C
(iv)Na,SO, ’ 2NaCl + conc H,SO4 Na,SO, + 2HCI
Anhydrous Na,SO, is called salt cake. It is the by product HCl industry,
) Na,CO, ’ It is prepared by 'Solvay Process'
The reactions take place during preparation of Na,CO,
NH, + C0, + H,0 = NH,HCO,
NaCl + NH, HCO, = NaHCO, NH,CI
2NaHCo,I99C Na,C0, +CO,‘ +H,0!
 (vi) KO2 (potassium super oxide)
K+ O2 ’ KO:
[lt is prepared by burning (orange powder) it in moisture free excess O,l
2K0;+ 2H,0 -’ 2KOH + H,0, + 0,
2KO)+ CO= K;CO,+O;
4KO;+ 2CO) = 2K,CO3+ 3O
(vii) KCO; (Pearl ash)
It is prepared using the following reactions
2KCl + H,SOspon KzSO4 + 2HCI
K,SO4 +C+CaCO, A, K,CO, +CaS + 2CO2
(viii) KNO, is prepared by the following exchange reaction
NaNO(aq.) + KCI (aq.) KNO, + NaCi
As solubility NaCl is less than KCI. Therefore the reaction proceeds in forward
direction.

" Li and Mg shows diagonal relationship as( ( o) , (polarising power)

" Li,SO, does not form alum as K,SO.
Anomalous properties of Li due to its
(a) small size (b) high electronegativity (c) absence of d orbitals in valence shell.
Alkaline earth metal
General ourtermost electronic configuration is ns2
(i) Ionisation enthalpy increases Be (i) atomic radius andionicradius increases
(ii) hydration of M²t(g) ion and Mg (i) electropositivity increases
hydration enthalpy increases Ca (ii) Reactivity increases
(iii) polarising power of M*" increases Sr (iv) Reducing character increases
Ba

" IE,and I-E,decreases down the group (1·E= lonisation enthalpy)

" IE,of alkali metal is less than that ofalkaline earth metal but I-E, is more than that ofalkaline
earth metal.
The stable oxidation state is + 2
" Hydration enthalpy (atCyt ae) decreases down the group as the size of the cation
increases and charge density decreases.
degree of hydration Be2+> Mg2t> Cat> Sr> Ba+
 [onic mobility increases from [Be(H,0).* to [Ba(H,0).]*
Melting point and boiling point of alkaline earth metals are greater than alkali metals due
to presence of 2 valence clectrons and formation of strong metallic bond.
Density and hardness of alkaline earth metals are greater than that of alkaline metals.
Density decreases from Be to Ca and then increases from Ca to Ba.
They form ionic compound due to low ionisation enthalpy.
The metals on their salt can give flame test. But Be and Mg do not give flame test as they
have high ionisation energy.
The alkaline earth metaland their cations are diamagnetic.
Ba.
The standard oxidation potential E' 2 2 t Gt fe) increases from Be to
Therefore reducing character increases from Be to Ba.
They form metal oxides on reaction with 0,
2M + O,= MO (normal oxide) [M = Mg, Ca]
M+0, = MO, (M= Ba, Sr)]
(Super oxide)
ionisation energy decreases.
" The reactivity increases down the group from Be to Ba as
alkali metal due to small size,
" Alkaline earth metals are less reactive than the corresponding
high charge, more ionisation energy.
$ MH, (M= Mg. Ca, Sr,
"They react with H,on heating to form metal hydride [M + H,
Ba]
Ca +H,
CaH, is called hydrolith
CaH, + 2H,0 ’ Ca(OH), +H,
" They react with N,form nitride
compound
Sr, Ba)
3M + N, ’ M, N, [M’ Be, Mg. Ca,
halides.
They react with halogen mnetal
M+ x, Mi,
(GBe*)
Due to high polarisation power of Be
BeCl, has covalent character. electrical conductivity of the
ionic character, melting point,
As we mnove down the group
metal halides increases.
least soluble in water. (among the alkaline earth
solvent. It is
BeCl,is soluble in organic
metal chlorides)
BeF,2 is more soluble than other alkaline earth metal fluorides due to high hydration
energy of Be2+
In vapour state BeCI, exists as monomer and dimer
C1 Be-CI
Cl - Be Be -C1[(BeCl,),]

SP hybridised
a
SP? SP?
hybridised.
In solid state it exists as polymeric chain. Here Be is sp³

Be

Ci
sp (BeCi,),
[(MgH,),]
BeH, and MgH, are covalent. They exists as [(BeH,)]&
H H

H H H

bond. (RCyTC sG The)

Here two Be atoms are linked by 3C- 2e hydrogen bridge
liquid NH, to form blue coloured
" Alkali metals and alkaline earth metals are soluble in
solution.
M+(rty)NH, ’ [M(NH,) J* + [e(NH,)J [M=alkali metal]
M+ (a+b)NH, ’ [M(NH) * +2[e(NH),J [M=alkaline earth metal]
Water solubility-’ Be(OH), <Mg(OH), < Ca(OH), < Sr(OH), <Ba(OH),
Basic strength-’ Be(OH), < Mg(OH),<Ca(OH), <Sr(OH),<Ba(OH),
(amphoteric)
" For metal carbonates
(i) BeCO, > MgCO,> CaCO, > SrCO, > BaCO, (water solubility)
BeCO, < MgCO, < CaCO, < SrCO, < BaCO, (thermal stability)
For metal Sulphate
6) BeSO, > MgSO, > CaSO,> SrSo, > BasO, (water solubility)
(ii) BeSO, <MgSO, < CaSO,<SrSo, <BasO, (thermal stability)
. Be reacts with NaOH to form
sodium beryillate
Be + 2NaOH + 2H,0’ Na,
. BeO is amphoteric in nature
[Be(OH),]+H,
BeO + 2HCI= BeCl, + H,0
BeO + 2NaOH = Na,BeO, + H,0
Compounds of alkaline earth metal
. CaSO,. 2H,0 ’ Gypsum
120°c
CaSO, 2H,0 CaSO, H,0,
200°C
CaSO,
Plaster of Paris
1100°c
CaSO, CaO + SO,
" BaSO, is used in medicine as contrast medium for stomach and intestinal X-rays

Beryllium halides are hygroscopic and form fumes in air due to hydrolysis

BeCl, +2H,0 -’ Be(OH), +2HCI 1 (fumes)

Be shows diagonal relationship with Al as a24A3+[4 = polarising power]
Be forms complexes due to its small size and high positive charge density. [BeF,]
 H,0,
H,0, is prepared by the action of cold dilute acids on metal peroxides like
BaO, or Na,0,.Hydrated BaO, (BaO,, 8H,0) is used otherwise insoluble
BaSO,isproduced on anhydrous BaO, during reaction with dil. H,SO,
Ba0, 8H,0 +H,SO, °G BaSO, +H,0, +8H,0
(dil)
BaO, +C0, +H,SO, 0G BaCO, J+H,0,
(Suspenssion of H,0)
Na,0, +H,so, 0°G Na,SO,+H,0,
(dil)

HPO, is preferred in place of dil H,S0, as H,PO, precipitates Ba² Completely.

Industrial method for preparation of H,O,
(a) H,0,is prepared by electrolysis of 50% ice cooled H,S0, (Conc.)
(b) H0, is prepared by auto oxidation of 2--ethylanthraquinol.
(c) Sometimes H,SO, and (NH.), SO, in 1:1 molar ratiois used for preparationof
H,0,
Storage of H,0,
H,0, is kept is plastic bottle in presence of astabilising agent like dil H,S0, as
H,PO, or glycerol.
H0, is decomposed in presence of alkalis, Sand. MnO, alumina. etc.
Strength of H,0,
The strength ofH,0, is expressed is terms of volumestrength, e.g. 10V, 20V etc.
20V H,0, means I ml H,0, gives 20 ml O, at STP on complete decomposition.
1% H0,= 3.294 Vol H,0,
1(N) H0, = 5.6 Vol. H,0,
 Properties
H,0, is slighty acidic.
H.0, - H.0 H0 HO.
HO, + H,0 H,0 +0,
H,0, + 2NaOH - Na,0, + 2H.0
HO,forms peroxide salt with metal hydroxides. This property is known as
peroxidising property.
H0,acts as an oxidising and as well as reducing agent. The oxidation state
of O' in H,0, is '-1'.It can be oxidised to Ö, and reduced to H,0.
HÔ HÕ
H0, =0, + 2H + 2e (1)
H,0, + 2H +2e = 2H,0 ’(ii)
H,0, oxidises pb's to pb'so, (white)
Oxidising Property
H,Ö,+ 2KÉ +2HCI =i+ 2KC1+ 2H,Þ
2K, (Fë(cN)]-H,0, - 2HCI =2 K, (Ye (CN)J +2KCI +2H,Þ
MnsO, +H,0, +2NaOH - MnO, +Na,SO, +2H,Þ
Cr,(SO,), + 3H,0, + 10 NaOH =2 Na, CrO, +3 Na, SO, + 8H,0
Reducing Property
2KMnO, -5 HÞ,+3H,S0,-2Mnso, +K,S0, +5 - 8H,0
K,Cr.0, - 4H,SO, +3H,0, Cr,(S0), +K,So, +7H,0 +30,
2KMnO, + 3H,0, = 2M nO, +30+2KOH +2H,0
2K, (Fe (CN),] +2KOH +H,Ö, =2 K, (Fe (CN),] +2H,0 +Q
CI, - H0, 2KOH=2KCI + O, + 2H,0
. H0, acts as an antichlor.
HO. -Þ- HÞ - 2Þ
HO, acts an bleaching agent.
H,0, -’ H,O [0}
 H,0, can form addition compounds.
Co(NH,), , H,0, (hyperol)
CH, = CH, + H,0, CH,CH,
OH OH
2 K,[Fe(CN),] +2KOH +H,Þ,
’2 K, (fe(CN),] +2H,0 +Þ
Marshall's acid

H, S, O,

HO OH

Caro's acid H,SO,

HO

s-o-o-0-H

potassium dichromate solution

Perchromic acid test :- When H,0, is added to
dilHSO, in presence of ether, and etheral layer becomes blue due to
acidified with
desolution of CrO, in ether.
2CrO, + K,SO, + 5H,0
K,Cr,0, + H,S0, + 4H,0, oranged coloured solution of pertitanic
HO. onreaction with acidified Ti0, from
2H,SO,
acid. Ti(SO), +H,0, +2H,0 = H,TiO,+
Cr=0
Structure of CrO,

Structure of H,0,
linear, and non planer structure with halfopen book structure. 94°48'
It has non H
and O O bonds is
For gaseous H,0, the angle between the O cover pages of an open book
The angle between two Haatoms which lie on the
is 111 30