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Be Mg Ca Sr Ba Ra
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
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.
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
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
MgO
CaO
SrO
BaO
2.4
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-
8.5 * 101
1.3 * 105
8.7 * 102
7.0 * 106
5.9 * 104
9.0 * 106
1.1 * 106
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.
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)
-HHyd = -yKJ
M+(aq) + A-(aq)
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
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)
These decompose to the more stable oxides. Mg(OH)2 (s) MgO (s) + H2O (s)
2.6