s-Block Elements

I Group Elements or alkali metals ( Li,Na,K,Rb,Cs,Fr)

General Electronic Configuration: [noble gas] ns1
PERIODIC PROPERTIES

1. Atomic and ionic radii or size:

 They have largest size in their period
Reason: Size decreases in a period due to increase in effective nuclear charge.
 Size increases as we move down the group.
Reason: Due to increase in the number of shells.
 They form monovalent cation by loosing one valence electron.
 Size of their cation is always smaller than the size of parent atom.
Reason: because ion has more effective nuclear charge. e.g. Na+ ion is smaller than Na atom.

2. Ionization Enthalpy or Ionization Energy or Ionization Potential: It is the energy required to remove
loosely bound outermost electron from a gaseous atom.
 Their ionization enthalpy is lowest in their period.
Reason: because of largest size in their period their outer most electron is loosely bound and easy to
remove by small amount of energy.
 II ionization enthalpy is always greater than I ionization enthalpy.
Reason: After removal of one electron it acquires noble gas configuration and it becomes very difficult to
remove 2nd electron.
 Moving down the group their ionization enthalpy decreases
Reason: As size of the atoms increases in the group. The force required to remove the electron decreases.

3. Hydration Enthalpy: It is the amount of energy released when one mole of gaseous ion changes to its
aqueous state.
 It is inversely proportional to the size of the cation. Li + > Na+ > K+ > Rb+ > Cs+. Therefore,
Li+ ion has maximum enthalpy of hydration. Due to this reason lithium salts are mostly
hydrated.

4. Density: Density is the mass per unit volume.

 They have lowest density in their period.
Reason: Because they are biggest in size in their period.
 It increases when we move down in the group.
Reason: Because the increase in atomic mass is more than the increase in atomic size.
As a result densities (mass/ volume) of alkali metals increases when we move down the
group.

5. Electropositive and Metallic Character: It is the tendency to loose electron.

 They are the most electropositive in their period
Reason: Due to lowest ionization enthalpy in the period
 Electropositive character increases down the group
Reason: Due to decrease in ionization enthalpy as we go down the group

6. Melting Point and Boiling Point: Their melting points and boiling points are low.
Reason: Due to presence of only one electron in their valence shell there is weak metallic bonding and
consequently melting points and boiling points are low.
The melting points decrease on descending the group as lattice energy decreases down the group generally.
Reason: The low melting point are attributed to their larger atomic size, due to which the binding energies of
their atoms in the crystal lattice are low. Further, in moving down the group, their atomic size increases and the
strength of metallic bond decreases which causes decrease in melting points. The boiling points of the
members of this group also follow the same order due to same reasons.

7. Flame Colouration: All the alkali metals impart colour to the flame.
Reason: Because their valence electron is loosely bound so it excites with the energy of flame to higher
level. When it comes back it emits extra energy which falls in visible range and give characteristic
colour. e.g. Lithium shows crimson red, Na = yellow, K = violet Rb = red violet and Cs shows blue
colours.

8. Photoelectric Effect: They eject their valence electron easily when light falls on their surface.
Reason: because their ionization energy is low therefore, they can eject their valence electron easily.
Due to this reason K and Cs are used as electrodes in photoelectric cells.
 CHEMICAL PROPERTIES

Reactivity increases when we move down in the group because of increase in size and decrease in
ionization energy.
1. Reactivity towards Air: Alkali metals get tarnished in presence of air due to formation of oxide (with oxygen)
and hydroxide (with moisture).
4Li + O2 → Li2 O (oxide)
2 Na + O2 → Na2O2 (peroxide)
K + O2 → KO2 (superoxide)
A smaller cation can stabilise a smaller anion while a larger cation can stabilise a larger anion in terms
of lattice energy effects. More the compatiblity between the ions more will be the lattice energy.
Li forms oxide, Na forms peroxides and bigger metals form super oxides.
 Li and Na can not form super oxides.
Reason: because they have small size and cannot stabilize superoxide ion (O 2-) which has a weak
negative field around it.
 Li forms nitride (Li3N) with nitrogen.
Reason: because of its smallest size and best reducing power. Li + size is most compatible with N 3- ion and
releases high lattice energy which overcomes the energy required for the formation of N3- ion.
Why is KO2 paramagnetic?
Reason: The superoxide is paramagnetic because of one unpaired electron in π*2p molecular
orbital.
2. Reactivity towards Water: Alkali metals form hydroxides and evolve hydrogen gas with water. This reaction
is highly exothermic.
2M +2H2O → 2MOH + H2
e.g. 2Na +2H2O → 2NaOH + H2
 They also react with proton donors like alcohols, ammonia and alkynes.

3. Reactivity towards Hydrogen: They react with hydrogen at very high temperature to give ionic hydrides in
which oxidation state of hydrogen is -1.

2M +2H2 → 2M+H- e.g. 2Na +H2 → 2Na+H-

4. Reactivity towards Halogens: Ionic halides (M+X- ) are formed.

2 M+ X2 → 2 M X e.g. 2Na + Cl2 → 2Na Cl
 lithium halides are covalent in nature.
Reason: Due to high polarization power of Li+ ion (due to small size).
 Among halides LiI is most covalent.
Reason: Because of small size of cation and biggest size of anion. High polarization.
 LiCl is soluble in organic solvents while NaCl not.
Reason: Because LiCl has covalent character because of polarization due to small size of lithium ion and
NaCl is electrovalent.

5. Reducing Nature: Due to low ionization energy, alkali metals are easily oxidized (remove electron) i.e.
show reducing properties. Reducing properties increases down the group because ionization energy decreases
down the group.
 Lithium is strongest reducing agent.
Reason: because of smallest size of Li+ ion its hydration enthalpy is highest which compensates for its high
ionization energy and sublimation energy.
M (s) M+(aq) + e-

(energy given) ∆subH ↓ ∆ hyd H (energy liberated)

M(g) → M+(g)
∆IEH
(energy given)

6. Solution in Liquid NH 3: The alkali metals dissolve in liquid ammonia giving deep blue solutions which
conduct electricity and are paramagnetic in nature.
M + (x+y) NH3 → [M(NH3)x] + + [e(NH3)y] -
Ammoniated Ammoniated
metal ion electrons
The blue colour of the solution is due to the ammonicated electrons which absorbs energy from red part of
visible region and impart blue colour to the solution. In concentrated solution, the blue colour changes to bronze
colour and becomes diamagnetic.

ANOMALOUS PROPERTIES OF LITHIUM

Lithium shows different properties from other alkali metals the reasons for anomalous behavior are:
(i) Extremely small size of lithium atom and its ion.
(ii) Greater polarizing power of lithium ion (i.e. charge/ radius ratio).

THE POINTS OF DIFFERENCE BETWEEN LITHIUM AND OTHER ALKALI METALS:

(i) Lithium is much harder than other alkali metals and has higher melting and boiling points than other alkali
metals.
(ii) It gives only oxides with oxygen while other alkali metals form peroxides and supreoxides.
(iii) It is strongest reducing agent.
(iv) Due to high hydration energy it forms hydrates LiCl. 2H2O whereas, other alkali metals do not form
hydrates.
(v) Li does not react with ethyne like other alkali metals.
(vi) It forms nitrides with nitrogen while other alkali metals do not form nitrides.
(vii) Compounds of lithium are less soluble in water while compounds of other alkali metals are fairly soluble in
water.

DIAGONAL RELATIONSHIP BETWEEN LITHIUM AND MAGNESIUM:

The first three elements of II period (Li, Be, B) show diagonal similarity with the elements (Mg, Al, Si) of III
period. This is called diagonal relationship.

II Li Be B

III Na Mg Al Si

Lithium and magnesium show similar properties due to: (similar charge/radius ratio)
( i) Their similar sizes
(ii) Almost similar electronegativity and ionization enthalpy.

POINTS OF SIMILARITY BETWEEN LITHIUM AND MAGNESIUM:

(i) Both lithium and Mg are harder than other elements in their respective group.
(ii) Both form nitride with nitrogen.
(iii) Their oxides and hydroxides are less soluble and hydroxides decompose on heating.
(iv) Both do not form superoxide.
(v) Both LiCl and Mg Cl2 are soluble in organic solvents.
(vi) Both for hydrates LiCl. 2H2O, MgCl2. 8H2O

GENERAL CHARACTERSTICS 0F ALKALI METAL COMPOUNDS:

A. Oxides and Hydroxides:

1. Li forms oxide, Na forms oxides and peroxides, K and other bigger metals form super oxides.
Reason: Because small cation can stabilize small anion while large cation can stabilize a large anion due to
lattice energy effect.
2. These are crystalline solid and strongly basic.
3. The order of basic character of hydroxides is:
LiOH<NaOH< KOH< RbOH< CsOH.
Reason: As size of atom increases (down the group) and ionization energy decreases, the bond between
metal and oxygen becomes weak, consequently, the basic character increases.

B. Halides:
1. Alkali metal halides are high melting crystalline solids. Their enthalpy of formation is highly negative.
2. The melting points follow the following trend:
Fluorides>chlorides> bromides> iodides.
Reason: because lattice enthalpy decreases as size of anion increases.
3. LiF is not soluble in water but it is soluble in organic solvents.
Reason: Because it has high lattice enthalpy. Due to high polarization power of Li+ ion (due to small size)

C. Carbonates and Bicarbonates:

1. Lithium shows exceptional behavior as its carbonates are not so stable and bicarbonates are liquid.
2. Thermal stability of carbonates follows the following order :
Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3.
Reason:
The compatibility of the ions increases as we go down the group.
M2CO3  M2O + CO2
As we go down the group the metal oxide becomes less stable than M 2CO3 due to bigger size of the
metal ion. Less the stability of metal oxide more will be the stability of its carbonates, so the stability of
M2CO3 increases down the group.
OR
As the electropositive character increases down the group, the stability of the carbonates and
hydorgencarbonates increases. Lithium carbonate is not so stable to heat; lithium being very small in
size polarises a large CO32- ion leading to the formation of more stable Li2O and CO2.
3. The same pattern is followed in case of hydrogen carbonates.
4. Li2CO3 is not thermally stable.
Reason: lithium ion is very small it can not hold big carbonate anion. Therefore, it decomposes to give
lithium oxide and carbon dioxide.

D. Salts of Oxo-Acids Oxo-acids: They are those in which the acidic proton is on a hydroxyl group
with an oxo group attached to the same atom e.g., carbonic acid, H2CO3 (OC(OH)2; sulphuric acid,
H2SO4 (O2S(OH)2). The alkali metals form salts with all the oxo-acids. They are generally soluble in
water and thermally stable. Their carbonates (M2CO3) and in most cases the hydrogencarbonates
(MHCO3) also are highly stable to heat.
II Group Elements ( Be, Mg, Ca, Sr, Ba, Ra) Except beryllium, these are known as
alkaline earth metals.
General Electronic Configuration: [noble gas] ns2
PERIODIC PROPERTIES

Atomic and ionic radii or size:

 They have smaller size than corresponding alkali metals.
Reason: Due to increase in effective nuclear charge.
 It increases as we move down the group.
Reason: due to increase in number of shells.
 They form bivalent cation by loosing two valence electrons
 Size of their cation is always smaller than the size of parent atom.
Reason: because ion has more effective nuclear charge. e.g. Mg2+ ion is smaller than Mg atom.

Ionization Enthalpy or Ionization Energy or Ionization Potential:

 Their ionization enthalpy is greater than corresponding alkali metals.
Reason: because of smaller size than corresponding alkali metals.
 II ionization enthalpy of alkaline earth metals is smaller than II ionization enthalpy of corresponding
alkali metals.
Reason: Because after removal of one electron it acquires configuration of alkali metals and easily remove
second electron to attains noble gas configuration.
 Moving down the group their ionization enthalpy decreases
Reason: as size of the atoms increases in the group.

Hydration Enthalpy:
 Hydration enthalpy of alkaline earth metals is larger than corresponding alkali metals.
Reason: It is inversely proportional to the size of the cation. As size of cation of alkaline earth metal is
smaller than alkali metal therefore, hydration enthalpy is more than the alkali metals.
 Alkaline earth metal salts are extensively hydrated because their ions are smaller than alkali metal ions.
e.g. MgCl2 .6H2O, CaCl2.6H2O
 Hydration enthalpy decreases on moving top to bottom in the group because size of cation
decreases.
Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+
Electropositive and Metallic Character:
 They are less electropositive than alkali metals.
 Electropositive character increases down the group.
Reason: due to decrease in ionization enthalpy.

Melting Point and Boiling Point:

 Their melting points and boiling points are higher than corresponding alkali metals.
 Reason: Because they have small size therefore, they are closely packed in their crystal lattice.

Flame Colouration: Alkaline earth metals impart colour to the flame. e.g. Ca, Sr and Ba impart brick red ,
crimson and apple green colour respectively.
 Be and Mg do not impart any colour to the flame.
Reason: Because Be and Mg atom are comparatively smaller and their ionization enthalpies are high. Hence,
their valence electrons do not excite by the energy of the flame.

CHEMICAL PROPERTIES

They are less reactive than alkali metals. Reactivity increases when we move down in the group because of
increase in size and decrease in ionization energy.
Reactivity towards Air: Alkaline earth metals react with air on heating. They form oxides and nitride of general
formula MO and M3N2 respectively ( M=Metal). Ba, Sr and Ra also form peroxide.

2M + O2 → 2MO (oxide; M= Be, Mg or Ca )

M + O2 → MO (peroxide; M= Ba, Sr or Ra)
2

Reactivity towards oxygen increases as we move down the group due to increasing electropositive character.

Reactivity towards Water: Except Be and Mg alkaline earth metals form hydroxides with cold water but they
are less reactive than alkali metals. Be do not react at all with water whereas Mg reacts with steam.

M +2H2O → M (OH) + H 2 2

e.g. Mg +2H O(steam) → Mg (OH)

2 + H2 2

Hydroxides are basic (Except that of Be) in nature and basic strength increases down the group.

Reactivity towards Hydrogen: They react with hydrogen at very high temperature to give ionic hydrides MH 2
in which oxidation state of hydrogen is -1.

M +H2 → MH 2

e.g. Be +H → BeH
2 2

BeH2 and MgH2 are covalent (because small size and high polarizing power of Be 2+ and Mg2+ ions) having
polymeric structure.

Reactivity towards Halogens: They combine with halogen at high temperature forming ionic halides (MX2).

M +X2 → MX 2

e.g. Mg +Cl → MgCl

2 2

The metal halides can also be prepared by the action of halogen acids on metals and their compounds like
oxides, carbonates and hydroxides.

Reaction with acids: They combine with acids and liberate hydrogen.

M + 2HCl → MCl + H 2 2 e.g. Ca + 2HCl → CaCl + H 2 2

Reducing Nature: Alkaline earth metals are good reducing agents but their reducing power is less than
corresponding alkali metals.
 Be is the best reducing agent amongst all alkaline earth metals.
Reason: because of smallest size of Be2+ ion its hydration enthalpy is highest which compensates for its high
ionization energy.
M (s) M2+(aq) + 2e-
(energy given) ∆subH ↓  ∆hyd H (energy liberated)
M(g) → M+ (g)
∆IEH
(energy given)

Solution in Liquid NH3: The alkaline earth metals dissolve in liquid ammonia giving deep blue balck solutions
which conduct electricity and are paramagnetic in nature.
M + (x+y) NH3 → [M(NH3)x] 2+ + 2[e(NH3)y] -
Ammoniated Ammoniated
metal ion electrons
The blue colour of the solution is due to the ammoniated electrons which absorbs energy from red part of visible
region and impart blue colour to the solution.

ANOMALOUS PROPERTIES OF BERYLLIUM:

Be shows different properties from other alkali metals the reasons for anomalous behavior are:
(i) Extremely small size of beryllium atom and its ion.
(ii) High ionization energy and electronegativity.
(iii) Absence of d-orbital.

THE POINTS OF DIFFERENCE BETWEEN BERYLLIUM AND OTHER ALKALINE EARTH METALS:

(i) Its compounds are covalent and get easily hydrolysed because of its small size.
(iii) It can not exhibit coordination number more than four because of absence of d-orbital. Others can have a
coordination number of 6.
(iv) The oxides and hydroxides of beryllium are amphoteric while oxides and hydroxides of other elements are
basic.
(v) It does not react with water while other metals react with water.

DIAGONAL RELATIONSHIP BETWEEN BERYLLIUM AND ALUMINIUM:

Elements of II period show similarity in properties with the elements present diagonally in III period. This is
called diagonal relationship.
II Li Be B

III Na Mg Al Si

The charge to radius ratio of Be2+ ion is nearly same as that of Al3 ion. Hence, it resembles aluminium.
Points of similarity are:
(i) Beryllium does not reacts with acids like aluminium because of the presence of oxide layer on their surface.
(ii) Be(OH)2 dissolves in excess of alkali to give beryllate ion [Be(OH) 2]2- just as aluminum hydroxide gives
aluminate ion [Al(OH)4]- .
(iii) Chlorides of both have Cl- bridged chloride structure in vapour phase. Both the chloride acts as Lewis acid
and are soluble in organic solvents (covalent character).
(iv) both have strong tendency to form complexes, BeF42- ,AlF63-

GENERAL CHARACTERSTICS 0F ALKALINE EARTH METAL COMPOUNDS:

A. Oxides and Hydroxides:

 Basic character of hydroxides follows the following order:
Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2.
Reason: As size of atom increases (down the group) and ionization energy decreases the bond between
metal and oxygen becomes weak, consequently, the basic character increases.
 They are very stable to heat.
Reason: Because their enthalpy of formation is very high.
 All oxides except beryllium oxide are basic in nature. Beryllium oxide is amphoteric in nature.
 The solubility, thermal stability and the basic character of these hydroxides increase.

B. Carbonates and Bicarbonates:

 Solubility of carbonates decreases down the group.

Reason: The size of the anions being much larger compared to cations, the lattice energy will remain
almost constant within a group. Since the hydration enthalpy decreases down the group due to increase in
cationic size and is not able to overcome the lattice enthalpy factor. Because hydration enthalpy ( as size of
cation increases) decreases.

Thermal stability increases down the group.

Reason: All the carbonates decomposes on heating to give carbon dioxide and oxide of the metal.
MCO3  MO + CO2
Because size of cation increases down the group and can hold a big anion As we go down the group
the metal oxide becomes less stable than M 2CO3 due to bigger size of the metal ion. Less the stability of metal
oxide more will be the stability of its carbonates, so the stability of M2CO3 increases down the group.

Sulphates: These are white solid and stable to heat.

 Solubility of sulphates decreases down the group. (same as carbonates)
 Reason: Because hydration enthalpy (as size of cation increases) decreases.

Why does the solubility of alkaline earth metal hydroxides in water increase down the group?
Solution: Among alkaline earth metal hydroxides, the anion being common the cationic radius will
influence the lattice enthalpy. Since lattice enthalpy decreases much more than the hydration enthalpy
with increasing ionic size, the solubility increases as we go down the group.
Why does the solubility of alkaline earth metal carbonates and sulphates in water decrease down
the group?
Solution: The size of anions being much larger compared to cations, the lattice enthalpy will remain
almost constant within a particular group. Since the hydration enthalpies decrease down the group,
solubility will decrease as found for alkaline earth metal carbonates and sulphates
Halides: Except beryllium halides all other alkaline earth metal halides are ionic in nature. Beryllium halides are
covalent and soluble in organic solvents.

Structure of Beryllium Chloride: In vapour phase it exists as chloro bridged dimer, but in solid state it has
chain structure.

Cl Cl
Cl
Be Be Be Be

Cl Cle
B Cl

Structure of BeCl2 in Solid State

Cl
Cl Be Be Cl

Be
Cl
Structure of BeCl2 in Vapour State