THE S-BLOCK ELEMENTS
Dr. Vatsala Soni
PGGC Sector -11
Chandigarh
Members of the s-Block Elements
IA IIA
Li Be
Na Mg
K Ca
Rb Sr
IA Alkali metals
Cs Ba
IIA Alkaline Earth
Fr Ra
metals
Chapter summary
Characteristic properties of the s-block elements
Variation in properties of the s-block elements
Variation in properties of the s-block compounds
Uses of compounds of the s-block elements
Characteristic properties of s-block
elements
Metallic character
Low electronegativity
Basic oxides, hydroxides
Ionic bond with fixed oxidation states
Characteristic flame colours
Weak tendency to from complex
Metallic character
High tendency to lose
e- to form positive ions
Metallic character
increases down both
groups
Electronegativity
Low nuclear Group I Group II
attraction for outer Li 1.0 Be 1.5
electrons
Na 0.9 Mg 1.2
Highly
electropositive K 0.8 Ca 1.0
Small Rb 0.8 Sr 1.0
electronegativity Cs 0.7 Ba 0.9
Fr 0.7 Ra 0.9
Basic oxides, hydroxides
Oxide Hydroxides Oxide Hydroxides
Li2O LiOH BeO Be(OH)2
Na2O, NaOH MgO Mg(OH)2
Na2O2 CaO Ca(OH)2
K2O2, KO2 KOH SrO Sr(OH)2
Rb2O2, RbOH BaO, Ba2O2 Ba(OH)2
RbO2
Cs2O2, CsOH
CsO2
Oxides, Peroxide, Superoxide
Reaction with water:
Oxide: O2- + H2O 2OH-
Peroxide: O22- + 2H2O H2O2 + 2OH-
Superoxide: 2O2- + 2H2O 2OH- + H2O2 + O2
. .-
.. .. 2-
:O:.O:
:O:O: Li does not form
.. ..
.. .. peroxide or super oxide
Super oxide Li2O2 Li2O + ½ O2
Peroxide ion
Hydroxides
Group I
hydroxides Li Na K Rb Cs
All are soluble, base strength
increase.
Group II
hydroxide Be Mg Ca Sr Ba
Solubility increase, from
Amphoteric to basic, base strength
increase
Predominantly ionic with fixed
oxidation state
Group I: Most electropositive metals.
Low first I.E. and extremely high second I.E.
Form predominantly ionic compounds with
non-metals by losing one electron.
Fixed oxidation state of +1.
Group II: Electropositive metals.
Low first and second I.E. but very high third
I.E.. Have a fixed oxidation state of +2.
Be and Mg compounds possess some degree
of covalent character.
Characteristic flame colours
Na+ Cl- (g) Na (g) + Cl (g)
Na(g) Na* (g)
[Ne]3s1 [Ne]3p1
Na*(g) Na(g) + h (589nm, yellow)
Flame test
Li deep red Ca brick red
Na yellow Sr blood red
K lilac Ba apple green
Rb bluish red
Cs blue
HCl(aq) sample
Weak tendency to form complex
Complex formation is a common feature of d-block
element. e.g. Co(NH3)63+
:NH3
s-block metal ions have
no low energy vacant H3N: :NH3
orbital available for Co
bonding with lone pairs H3N: :NH3
of surrounding ligands,
:NH3
they rarely form
complexes.
Variation in properties of elements
Atomic radii
Ionization enthalpies
Hydration enthalpies
Melting points
Reactions with oxygen, water, hydrogen and
chlorine
Atomic radii (nm)
Li 0.152 Be 0.112
Na 0.186 Mg 0.160 Fr
K 0.231 Ca 0.197
Ra
Li
Rb 0.244 Sr 0.215
Cs 0.262 Ba 0.217 Be
Fr 0.270 Ra 0.220
Ionization Enthapy
Group I 1st I.E. 2nd I.E.
Group I 1st I.E. 2nd I.E. 3rd I.E.
Li 519 7300
Be 900 1760 14800
Na 494 4560
Mg 736 1450 7740
K 418 3070
Ca 590 1150 4940
Rb 402 2370
Sr 548 1060 4120
Cs 376 2420
Ba 502 966 3390
Ionization Enthalpy
1st I.E.
2000
600 Be+
Li
500 Na 1500
2nd IE
400 K
Rb Ca+
Cs 1000
300 Be Ba+
500 Ca
1st IE Ba
Ionization Enthalpy
Group I
1. Have generally low 1st I.E. as it is well shielded
from the nucleus by inner shells.
2. Removal of a 2nd electron is much more difficult
because it involves the removal of inner shell
electron.
3. I.E. decreases as the group is descended.
As atomic radius increases, the outer e is further
away from the well-shielded nucleus.
Ionization Enthalpy
Group II
1. Have low 1st and 2nd IE.
2. Removal of the 3rd electron is much more difficult
as it involves the loss of an inner shell electron.
3. IE decrease as the group is descended.
4. IE of the group II is generally higher than group I.
Hydration Enthalpy
M+(g) + aqueous M+(aq) + heat
-600
M+ -300
Li+ Na+ K+ Rb+ Cs+
Hydration Enthalpy
-2250
-600
-2000
-1750
-300
-1500
Li+ Na+ K+ Rb+ Cs+ Be2+ Mg2+ Ca2+ Sr2+ Ba2+
Hydration Enthalpy
General trends:
1. On going down both groups, hydration enthalpy
decreases.
(As the ions get larger, the charge density of the
ions decreases, the electrostatic attraction between
ions and water molecules gets smaller.)
2. Group 2 ions have hydration enthalpies higher
than group 1.
( Group 2 cations are doubly charged and have
smaller sizes)
Variation in Melting Points
Be
1250
1000
Ca
Sr
750 Ba
Mg
500
250 Li
Na K Rb
Cs
10 20 30 40 50 60
Variation in Melting Points
Strength of metallic bond depends on:
1. Ionic radius
2. Number of e- contributed to the electron sea per atom
3. Crystal lattice structure
Note: The exceptionally high m.p. of calcium
is due to contribution of d-orbital participation
of metallic bonding.
Variation in Melting Points
Group I Structure Group II Structure
Li B.C.C. Be H.C.P.
Na B.C.C. Mg H.C.P.
K B.C.C. Ca C.C.P.
Rb B.C.C. Sr C.C.P.
Cs B.C.C. Ba B.C.C.
Reactions with oxygen
S-block elements are strong reducing agents.
Their reducing power increases down both groups.
(As the atomic size increases, it becomes easier to
remove the outermost electron)
S-block elements reacts readily with oxygen.
Except Be and Mg, they have to be stored under
liquid paraffin to prevent contact with the atmosphere.
Reactions with oxygen
Normal Peroxide Superoxide
Oxide
Structure .. 2- .. .. 2- . .-
:O: :O-O: :O:.O:
.. .. .. .. ..
Formed by Li and Na and Ba K, Rb, Cs
Group II
Reaction with water
M(s) M+(aq) + e-
H2O(l) + e- OH-(aq) + ½ H2(g)
Li -3.05 volt
Na -2.71
K -2.93 Be -1.85 volt
Rb -2.99 Mg -2.38
Cs -3.20 Ca -2.87
Sr -2.89
Ba -2.90
Energetic vs. Kinetic Factor
Reaction with hydrogen
All the s-block elements except Be react directly with
hydrogen.
2Na(s) + H2(g) 2NaH(s)
Ca(s) + H2(g) CaH2(s)
The reactivity increases down the group.
Only BeH2 and MgH2 are covalent, others are ionic.
Reaction with chlorine
All the s-block metals react directly with chlorine
to produce chloride.
All group I chlorides are ionic.
BeCl2 is essentially covalent, with comparatively low
m.p.
The lower members in group II form essentially ionic
chlorides, with Mg having intermediate properties.
Although lithium has highly negative Eo, it only
reacts slowly with water. This illustrates the importance
of the role of kinetic factors in determining the rate
of a chemical reaction.
Lithium has a higher m.p., this increases the activation
energy required for dissolution in aqueous solution.
It does not melt during the reaction as Na and K do, and
thus it has a smaller area of contact with water.
Variation in properties of the
compounds
Reactions of oxides and hydroxides
Reactions of chlorides
Reactions of hydrides
Relative thermal stability of carbonates and
hydroxides
Relative solubility of sulphate(VI) and hydroxde
Reactions of oxides and hydroxides
1. All group I oxides reacts with water to form
hydroxides
Oxide: O2- + H2O 2OH-
Peroxide: O22- + 2H2O H2O2 + 2OH-
Superoxide: 2O2- + 2H2O 2OH- + H2O2 + O2
2. All group I oxides/hydroxides are basic and the
basicity increases down the group.
Reactions of oxides and hydroxides
3. Group II oxides/hydroxides are generally less basic
than Group I. Beryllium oxide/hydroxide are
amphoteric.
Reactions of chlorides
1. All group I chlorides are ionic and readily
soluble in water. No hydrolysis occurs.
2. Group II chlorides show some degree of covalent
character.
Beryllium chloride is covalent and hydrolysis to
form Be(OH)2(s) and HCl(aq).
Magnesium chloride is intermediate, it dissolves and
hydrolysis slightly.
Other group II chlorides just dissolve without
hydrolysis.
Reactions of hydrides
They all react readily with water to give the
metal hydroxide and hydrogen due to the
strong basic property of the hydride ion, H:-
H:-(s)+ H2O(l) H2(g)+ OH-(aq)
Hydride ions are also good reducing agent.
They can be used to prepare complex hydrides
such as LiAlH4 and NaBH4 which are used to
reduce C=O in organic chemistry.
Thermal Stability
Thermal stability refers to decomposition of the
compound on heating. Increased thermal stability
means a higher temperature is needed to decompose
the compound.
Thermal Stability of carbonates
Li2CO3 Li2O + CO2 ( at 700oC)
All other group I carbonates are stable at ~800oC
BeCO3 BeO + CO2 ( at 100oC)
MgCO3 MgO + CO2 ( at 540oC)
CaCO3 CaO + CO2 ( at 900oC)
SrCO3 SrO + CO2 ( at 1290oC)
BaCO3 BaO + CO2 ( at 1360oC)
Thermal Stability of hydroxides
All group I hydroxides are stable except LiOH
at Bunsen temperature.
Be(OH)2(s) BeO(s) + H2O(g) H = +54 kJ/mol
Mg(OH)2(s) MgO(s) + H2O(g) H = +81 kJ/mol
Ca(OH)2(s) CaO(s) + H2O(g) H = +109 kJ/mol
Sr(OH)2(s) SrO(s) + H2O(g) H = +127 kJ/mol
Ba(OH)2(s) BaO(s) + H2O(g) H = +146 kJ/mol
Thermal stability
1. Carbonates and hydroxides of Group I metals
are as a whole more stable than those of Group II.
2. Thermal stability increases on descending the group.
3. Lithium often follow the pattern of Group II rather
than Group I.
This is an example of the diagonal relationship.
Explanation of Thermal Stability
1. Charge of the ions
2. Size of the ions
3. Compounds are more stable if the charge increases
and size decreases.
4. For compounds with large polarizable anions, thermal
stability is affected by the polarizing power of the
cations.
Explanation of Thermal Stability
+ -
Decreasing Increasing
+ -
polarizing stability
power
+ -
Explanation of Thermal Stability
O
Mg2+ - :O C Mg2+ O2- + CO2
O:-
-:O H
Mg2+ Mg2+ O2- + H2O
-:O H
Explanation of Thermal Stability
MgCO3 MgO
BaO
MgO
BaCO3 BaO
Relative solubility of Group II
hydroxides
Compound Solubility / mol per 100g
water
Mg(OH)2 0.020 x 10-3
Solubility of hydroxides
Ca(OH)2 1.5 x 10-3 increases down the group.
Sr(OH)2 3.4 x 10-3
Ba(OH)2 15 x 10-3
Solubility of Group II sulphates
Compound Solubility / mol per 100g
water
MgSO4 3600 x 10-4
Solubility of sulphates
CaSO4 11 x 10-4 increases up the group.
SrSO4 0.62 x 10-4
BaSO4 0.009 x 10-4
Explanation of solubility
aqueous
MX(s) M+(aq) + X-(aq)
H solution
-H lattice H hydration
M+(g) + X-(g)
H solution = -H lattice + H hydration
Explanation of solubility
1. Group I compounds are more soluble than Group II
because the metal ions have smaller charges and
larger sizes. H lattice is smaller, and H solution is
more exothermic.
H solution = -H lattice + H hydration
Explanation of solubility
H solution = -H lattice + H hydration
2. For Group II sulphates, the cations are much smaller
than the anions. The changing in size of cations does
not cause a significant change in H lattice (proportional
to 1/(r+ + r-).
However, the changing in size of cations does cause
H hydration (proportional to 1/r+ and 1/r-) to become less
exothermic, and the solubility decreases when
descending the Group.
SO42- SO42-
MgSO4 SrSO4
Explanation of solubility
H solution = -H lattice + H hydration
3. For the smaller size anions, OH-.
Down the Group, less enthalpy is required to
break the lattice as the size of cation increases.
However the change in H solution is comparatively
smaller due to the large value of 1/r- .
As a result, H solution becomes more exothermic
and the solubility increases down the Group.
Mg(OH)2 Sr(OH)2
Uses of s-block compounds
Sodium carbonate
Manufacture of glass
Water softening
Paper industry
Sodium hydrocarbonate
Baking powder
Soft drink
Uses of s-block compounds
Sodium hydroxide
Manufacture of soaps, dyes, paper and drugs
To make rayon and important chemicals
Magnesium hydroxide
Milk of magnesia, an antacid
Calcium hydroxide
To neutralize acids in waste water treatment
Strontium compound
Fireworks, persistent intense red flame
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