Chemistry of the Elements

GROUP TWO ELEMENTS

Be Mg Ca Sr Ba Ra

FIGURE 2.1 Elements In Group Two (2)

Beryllium Be Electronic Structure Electronegativity 1st I.E / KJ mol-1 2nd I.E / KJ mol-1 M.P / oC B.P / C
o

Magnesium Mg [Ne] 2s2 1.2 738 1500 650 1117 0.16 +2 -2.37

Calcium Ca [Ar] 4s2 1.0 590 1100 850 1492 0.20 +2 -2.87

Strontium Sr [Kr] 4s2 1.0 550 1100 770 1367 0.21 +2 -2.89

Barium Ba [Xe] 6s2 0.9 500 1000 710 1673 0.22 +2 -2.90

[He] 2s2 1.5 899 1800 1283 2477 0.11 +2 -1.85

Atomic Radius / nm Oxidation No. Eom+ / mV

TABLE 2.1 Elements In Group Two (2)

2.1

FAJANS RULE
An ionic compound will have a high degree of covalency if: The positive ion is small and highly charged. The negative ion is large (highly polarisable) Generally, covalency is promoted by small cations and large anions.

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Chemistry of the Elements For example, the beryllium ion, Be2+, is so small that it manages to polarize any negative ion to such a degree that its compounds are predominantly covalent. Group II elements are good reducing agents, they give ionic compounds, their oxides and hydroxides are basic and they give hydrogen with oxides. The exception is beryllium. One reason why beryllium is different is that its electrons are not strongly shielded from its nucleus. The radius of the Be2+ ion is extremely small, and it represents a very dense centre of positive charge. Beryllium also has a higher electronegativity than the other elements. Hence, the compounds it makes with non metals should have less ionic character. The solutions of beryllium compounds suffer hydrolysis and are amphoteric rather than completely basic. Beryllium will dissolve in alkali. This is something that magnesium and the other metals in the Group II will not do: Be (s) + 2OH- (aq) BeO22- (aq) + H2 (g)

The product BeO22-, is the berylleto ion, which is better represented in solution as the tetrahydroxoberyllate III ion Be(OH)42-. In its amphoteric behaviour it resembles aluminum in group III.

2.2

REACTIONS OF THE GROUP (II) ELEMENTS

REACTANT Water Be No reaction Mg Slow, rapid with steam. Mg(s) + H2O
(g)

REACTION

MgO(s) + H2 (g)

Ca reacts steadily. Sr and Ba reacts more than Ca Oxygen Dilute Acid All tarnish in air, oxide forms. All burn readily in air. Be, Mg Steadily Ca vigorously St, Ba More vigorous. Halogens Nitrogen All form halides. All form nitrides (except Be). On additon of water nitrides give ammonia. Mg + N2
(s)

(s)

(g)

Mg3N2

(s) (aq)

Mg3N2
TABLE 2.2 Reactions Of The Elements

+ 6H2O Mg(OH)2

+ 2NH3

(g)

2.3

BEHAVIOUR OF OXIDES WITH WATER

The behaviour of the oxides with water:

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Chemistry of the Elements

MgO

CaO

SrO

BaO

Increasing Basic Character

2.4

SOLUBILITIES OF THE SULPHATES

Solubilities of sulphates decrease down the group, also for carbonates, and chromates and hydroxides increases.

SOLUBILITIES AT 25 oC Element Be Mg Ca Sr Ba SO423.79 * 10-1 S1.83 * 10-1 4.66 * 10-3 7.11 * 10-5 9.43 * 10-7 1.3 * 104

CO321

OH-

CrO42-

2.0 * 10-5 1.6 * 10-3 3.3 * 10-2 2.4 * 10-2

8.5 * 101

1.3 * 105

8.7 * 102

7.0 * 106

5.9 * 104

9.0 * 106

1.1 * 106

Decrease Decrease Increase

TABLE 2.3 Solubilities Of Sulphates

Increase

Solubilities are determined by two factors: 1). The ability of crystal lattices to break up. It should be noted that the lattice is very hard to break. HoLatt(D) Highly endothermic.

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Chemistry of the Elements

2).

The release of energy. Much energy is released when the ions are hydrated. HoHyd Highly exothermic. When an ionic compound dissolves in water, the following process occurs: M+A- (s) + (aq) This process is a result of two stages: First: Separation of the ions in the solid: M+A- (s) M+ (g) + A- (g) M+ (aq) + A- (aq)

This is the reverse of lattice formation and requires input of the lattice energy. Second: Involves hydration of the separation ions by water. M+ (aq) + A- (aq)

M+ (g) + A- (g) + (aq)

M+ (g) + A- (g) + (aq)

-HLatt MA(s) = xKJ

-HHyd = -yKJ

M+(aq) + A-(aq)

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Chemistry of the Elements

FIGURE 2.2 The Relationship Between Lattice Energy, Hydration Energy And Enthalpy Change

THE RELATIONSHIP BETWEEN LATTICE ENERGY, HYDRATION ENERGY AND ENTHALPY CHANGE OF SOLUTION As the ionic radii of M+ and A- increases, the enthalpy change in both of the stages above decreases. The reverse lattice energy process becomes less endothermic and the hydration process exothermic. The cancellation effect of both processes is not always reliable to predict solubilities. The general pattern and trends in the solubility group II salts are: Group II cations containing anions with a charge of -1 (e.g. Cl, NO3-) are generally soluble, except for the hydroxides. Group II cations containing anion with a charge of -2 (e.g. SO42-,CO32-) are generally insoluble, except for some magnesium and calcium salts. The distinct trend of the sulphates: Beryllium and Magnesium (Very Soluble), Calcium (Sparingly Soluble), Strontium and Barium (Insoluble).

2.5

THERMAL DECOMPOSITION OF THE CARBONATES AND NITRATES

The stability if the salt M+A-(s) is dependent on the size of its ions and the charge on these ions. The greater the charge, the stronger is the attraction between the ions and the more stable is M+A- (s). The smaller the ions become, the closer they can approach each other in the solic crystal and the more stable is M+A- (s). Also, when large anions such as CO32- decompose on heating to form smaller anion such as O2-, the crystal containing the latter will generally be more stable. This is because the charge density on the small O2- in will be greater than that on a larger CO32ion, thus O2- will be more strongly attracted to the cations in the crystal and get even closer. NITRATES Group II nitrates and LiNO3 decompose on heating to form their corresponding oxide, e.g. Mg(NO3)2 (s) LiNO3 (s) MgO (s) + 2NO2 (s) + O2 (g) LiO (s) + 2NO2 (s) + O2 (g)

The nitrates achieve greater stability by decomposing to much smaller oxides ion. CARBONATES Group II carbonates and Li2CO3 decomposes to form their corresponding oxide. They achieve thermal stability by forming the O2- ion. MgCO3 (s) Li2CO3 (s) HYRDOXIDE MgO (s) + CO2 (g)

Li2O (s) + CO2 (g)

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Chemistry of the Elements

These decompose to the more stable oxides. Mg(OH)2 (s) MgO (s) + H2O (s)

LiOH decomposes at about 950 oC.

2.6

USES OF MAGNESIUM AND CALCIUM COMPOUNDS

MAGNESIUM AND CALCIUM Calcium Hydroxide (slaked lime). The solution is called lime water. (a) Treatment of fields which are too acidic for healthy plant growth. (b) Mortar a mixture of slaked lime, sand and water. (c) Manufacture of Calcium Hydrogen Sulphate Ca(HSO4)2. The paper industry needs this to remove lignin from woods and leave cellulose, ready to be made into paper. (d) Reaction with chlorine to form bleaching powders, Ca(OCl)2, CaClz. This is a useful source of chlorine, which it liberates readily when an acid is added. CALCIUM OXIDE (a) Neutralizes excessive acidity. (b) Used to dry ammonia. (c) It is refractory, that is, it will not melt even when heated to a very high temperature. MAGNESIUM OXIDE (a) Use as refractory lining in furnaces. CALCIUM CARBONATE (a) Used in the Solvay process for manufacture of sodium carbonate. (b) Used in the iron and steel industry. (c) Used in the glass industry. (d) Used in the cement industry.

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