GROUP II (Alkaline Earth Metals)

Group II elements form part of the s-block elements as they all have two outermosts electrons. 1s22s2 1s22s22p63s2 1s22s22p63s23p64s2 1s22s22p63s23p63d104s24p65s2 1s22s22p63s23p63d104s24p6 4d105s25p66s2

4Be 12Mg 20Ca 38Sr 56Ba

1. The group II elements tend to loose 2 electrons to reach a rare gas structure. Group II elements therefore show oxidation state of +2. Group II elements cannot show any higher oxidation state as too much energy is required to disturb the inert structure. 2. The tendency to loose 2 electrons makes group II elements reducing agents. Due to increase in the number of shells and shielding effect, the metals become good electron donors and hence better reducing agents. The reducing properties can be shown by electrode potential values. Mg - 2e Mg2+ Ca - 2e Ca2+ Sr - 2e Sr2+
2+

Down the group. There is increase in oxidation potential. Therefore there is an increase in reducing power.

Ba - 2e Ba

Diagonal relationship in the periodic table

Elements in the group II do not show all characteristics of the group. Instead, they show more similarities to elements that are diagonally placed with respect to them.

Decrease in atomic radius and increase in electronegativity GROUP I II III IV V

PERIOD 2

Li

Be

N Decrease in atomic radius and Increase increase decrease in electronegativity These are the reasons for diagonal relationship

PERIOD 3

Na

Mg Al

Si

PERIOD 4

Ca

Ga

Ge

Diagonal relationship

e.g Beryllium does not form Be2+, which will be small and highly charged (hence very polarizing). Beryllium compounds are mainly covalent, e.g. BeCl 2 is covalent. Beryllium resembles aluminium by diagonal relationship. Beryllium resembles aluminium in many respects and is atypical in group II. All oxides of Group II are basic while BeO is amphoteric, like Al 2O3. Similarly BeCl2 polymerises while AlCl3 dimerises. 3. The last member of the group II is Radium (Ra), a radioactive element whose chemistry will not be considered.

Trends down Group II

Be Mg Ca Sr Ba

Increase in nuclear charge. The shielding effect counter balance the increase in nuclear charge. Decrease energy in first ionisation

1. Increase in atomic radius 2. Decrease in ionisation energy 3. Better electron donors down the group. Hence they become better reducing agents.

Be Mg Ca Sr Ba

1. Atomic radius increases 2. Strength of metallic bond decreases as electrons are less strongly held by the positive ions 3. Melting and Boiling point increase.

1. Metallic bond becomes weaker 2. Metals become mechanically weak 3. Metals become softer.

Reaction of Group II elements 1. With water Beryllium Beryllium has no reaction with water or steam even at red heat. Magnesium Magnesium burns in steam to produce magnesium oxide and hydrogen. Mg(s) + H2O(g) MgO(s) + H2(g) Very clean magnesium has a very slight reaction with cold water. The reaction soon stops because the magnesium hydroxide formed is almost insoluble in water and forms a barrier on the magnesium preventing further reaction. Mg(s) + 2H2O(g) Mg(OH)2(s) + H2(g) Calcium, strontium and barium

These all react with cold water with increasing vigour to give the metal hydroxide and hydrogen. The equation for the reactions of any of these metals would be: X(s) + 2H2O(l) X(OH)2(aq or s) + H2(g) 2. With air Group II metals burn in oxygen to form a simple metal oxide with the exception of Beryllium which has a very strong (but very thin) layer of beryllium oxide on its surface, and this prevents any new oxygen getting at the underlying beryllium to react with it. 2X(s) + O2(g) 2XO(s) Trends in properties of compounds of elements down Group II A. Thermal stability of carbonates, nitrates and hydroxides of Group II 1. The effect of heat on the Group II carbonates Consider the carbonates of Group II elements and their respective decomposition temperature based on the general equation given below MCO3 MO + CO2

Decomposition temperature/ K BeCO3 MgCO3 CaCO3 SrCO3 BaCO3 BeO + CO2 MgO + CO2 CaO + CO2 SrO + CO2 BaO + CO2 370 430 1170 1550 1630

Decomposition temperature decreases down the group as the carbonates become increasingly stable. Explanation

Be

2+

C
-

An isolated carbonate ion can be represented as:

-

Distortion due to neighbouring Be2+ Mg

2+

C
-

Ca2+

EVEN DISTRIBUTION OF ELECTRON CLOUD (NO DISTORTION OF CLOUD)

Sr2+

Very slight distortion of electronic cloud

-

Ba2+
-

C
O

1. All the group II elements form +2 oxidation state. 2. The ionic radius increases. 3. The polarisation power of a cation is proportional to its charge and inversely proportional to its size (size and charge give rise to charge density) 4. The polarisation power of Be2+> Mg2+>Ca2+>Sr2+>Ba2+, so that the degree of distortion of the neighbouring carbonate ion is more pronounced with Be2+ than with Ba2+ as shown above. 5. For BeCO3 , there is a decrease in stability of the ion as the latter is no longer planar so that the carbonate ion readily decomposes to a more stable oxide ion and carbondioxide.

2. The effect of heat on the Group II hydroxides The hydroxides of group II metals all decompose according to the equation below: M(OH)2 MO + H2O , where M is a group II element E.g. Mg(OH)2 MgO + H2O Thermal stability again increases down the group.

3. The effect of heat on the Group II Nitrates The Group II nitrates become similarly more stable down the group so that decomposition temperature again increases. The Group II nitrates decompose according to the following general equation: 2M(NO3)2 2MO + 4NO2 + O2 , where M is a Group II element E.g.1. 2Mg(NO3)2 2MgO + 4NO2 + O2 E.g.2. 2Ca(NO3)2 2CaO + 4NO2 + O2 Note that lithium compounds show more similarity to compounds of Group II elements. Lithium compounds show diagonal similarity to Magnesium compounds.

B. Solubility of Group II sulphates, oxalates and chromates Down Group II , sulphates become less soluble. MgSO4 CaSO4 SrSO4 BaSO4 Soluble Sparingly soluble Insoluble Insoluble

Explanation

MSO4 (s) - H lattice energy

H solution

M2+(aq) + SO42-(aq) Hhydration (SO42-(g) )

Hhydration (M2+(g) )

M2+(g) + SO42-(g) Solubility = H , solution which depends on - H

lattice energy

and

H hydration (M 2+ (g) )

and H hydration (SO 4 2- (g) )

SO42Mg2+

r-

r+

Z+ Z1. The lattice energy r++ rDown the Group II sulphates, the charge of the cation ( Z+) and that of the anion (Z-) remain the same. The size of the anions also remain the same (r -). Group II sulphates have cations radius (r +) that shows very + small increase so that the overall r + r remains constant. 2. The hydration energy of the anion 1 / ranion . Since the size of the anion remains the same the hydration energy of the sulphate remains same. SO42-

SO42Ca2+

r-

Sr

2+

r-

3. The hydration energy of the cation 1 / rcation . Down the group the size of the cation increases (though that the increase is slight) and thus the size of the hydration energy decreases.

r+
Overall lattice energy and hydration energy of the anion have no effect on the solubility of the sulphates. The hydration energy of the cation decreases so that the solubility also decreases.

SO42Ba2+

r-

r+

Similar solubility of other salts of Group II with large anions namely oxalates and chromates i.e. solubility decreases

e.g Magnesium oxalate is soluble while barium oxalate is not. The shape and bonding in ethanedioate and chromate ion is shown below.
-O O -O O

C Cr C
-O O -O

Oxalate or ethandioate ion

Chromate ion

C. Solubility of Group II hydroxides and oxides The hydroxides and oxides become more soluble down the group. Mg(OH)2 Ca(OH)2 Sr(OH)2 Ba(OH)2 - Almost insoluble - Sparingly soluble (lime water) - Soluble - Completely soluble (Baryta water)

Explanation Just like the case of solubility of Group II sulphates, the same factors affect the solubility of Group II hydroxides and oxides i.e Factor 1. the lattice energy of the salt Factor 2. the hydration of anion Factor 3. the hydration of cations

For Group II hydroxides and oxides: Factor 1 changes because the size of anion is small. Down the group II hydroxides (or oxides) the overall sum of r+ + r increases so that lattice energy decreases and hence the conversion of M(OH)2(s) M2+ (g) + 2OH-(g) decreases (hence facilitating the solubility).

Factor 2 remains the same Factor 3 is the same as for solubility of Group II sulphates.

USES OF GROUP II COMPOUNDS 1. Agriculture (Calcium carbonate and calcium hydroxide) Lime is used t control pH of soil and hence to enhance the uptake of essential cations 2. Magnesium - oxide is used as refractory materials [High melting point and low conductivity] 3. Calcium carbonate and calcium hydroxide In cement as building material