CHAPTER 10

Discussion on : Mg, Ca, Sr, Ba Anomaly : Be Not included : Ra (radioactive)

Radium

Mg

1. Atomic & Ionic Radius

Atomic radius increases down the group due to its increase in the number of shells/energy levels.
Decrease in the effective nuclear charge which is influenced by the increase in the screening effect done by the inner orbitals.

Ionic radius is smaller than the atomic radius :after losing the outermost shell electron(s), there is one electron shell less in the cation than in the atom.
Increase in ENC

2. The ionisation energies decrease down the Group atomic sizes increase down the group the outermost shell electron(s) is/are further away from the nucleus, better shielded by inner electron shells. less attractive force experienced less energy is required to remove the electrons Because of the high I.E., Be forms a few covalent compounds instead of forming Be2+ respectively.

3. Melting Point

 decreases going down the group

the atomic size of the elements increases attraction between positively charged nucleus and delocalised electron sea becomes weaker

metallic bond is weaker

 irregularity in the general decrease in melting point down Group II (Mg Ba) elements
different metallic crystal structures of the Group II elements

Group Crystal II metal structure Be Mg Ca Sr Ba Ra h h f f b

 All have low electronegativity values

the outermost electron shell is effectively shielded by inner electron shells. - Low effective nuclear charge. Decrease when going down the group the outermost electron shell are further away from nucleus - increase in shielding effect.
Group II element
Be Mg Ca Sr Ba Ra

Electronegativity
1.5 1.2 1.0 1.0 0.9

1. Reaction with Oxygen All alkaline earth metals burns in oxygen to form its oxide which are white solids. Be, Mg T, Ca, Sr, Ba rt The metals reduce O2 to form oxides:

2E(s) + O2(g) 2EO(s) 2Mg(s) + O2(g) 2MgO(s) 2Ca(s) + O2(g) 2CaO(s)

2Ba(s) + O2(g) 2BaO(s)

2. Reaction with Water All Group II metals (except Be) react with H2O to form metal hydroxides and H2 gas (Mg reacts with hot water). The reactivity with water increases down the group due to the increase in the reducing strength of these metals. 2E(s) + H2O(l) 2E2+(aq) + 2OH-(aq) + H2(g) (E = Ca, Sr, Ba) Ca(s) + 2H2O(l) Ca(OH)2(aq) + H2(g) Sr(s) + 2H2O(l) Sr(OH)2(aq) + H2(g)

 Group II oxides (except BeO) react with H2O to form a weakly alkaline solution EO(s) + H2O(l) E2+(aq) + 2OH-(aq)

e.g. CaO(s) + H2O(l) Ca(OH)2(aq) (weakly alkaline)

The basicity of all Group II oxides increases down the group SrO & BaO can form peroxide

SrO2 & BaO2

# BeO is amphoteric

Group II element

Mg Ca Sr Ba

Rx with water Slowly with steam Fast with hot water Vigorous with cold water Vigorous with cold water

 Carbonates, nitrates and hydroxides of Group II metals undergo decomposition on strong heating to give oxides (more stable) e.g.

MgCO3(s) MgO(s) + CO2(g) 2Ca(NO3)2(s) 2CaO(s) + O2(g) + 4NO2(g) Sr(OH)2(s) CaO(s) + H2O(g)

 The higher the thermal stability of a compound, the higher is the temperature needed to decompose it The thermal stability of ionic compounds depends on:

(1)
(2)

charges &
sizes of ions

 Compound with large polarisable anion (large electron cloud), the thermal stability depends on the polarising power (charge density) of cations The stronger the polarising power, the electron cloud of anion will be distorted to greater extent The compound tends to be less thermal stable

 oxide ions can approach the cations more closely. Increase the strength of ionic bonds in oxides making them more stable. Polarisability of large anion such as CO32- by the highly charged G2 cations weakens C-O bonds O2- & CO2.

 going down G2, size of cations increases charge density & polarising power decreases.

Stability of CO32- towrds heat increases with proton number. Applies to nitrates & hydroxides.

Effect of sizes of cations on thermal stability of compounds

Relative sizes of the G2 cations & the anions

CO32-

2+

2+

NO3-

2+

OH-

2+

O2-

Summary of thermal decomposition of carbonates of G2 cations

O
2+

O
2+

O- C

O-

C O-

O-

2+

O2-

+OCO

BeSO4 ,MgSO4 soluble in water

CaSO4 sparingly soluble

SrSO4,BaSO4 insoluble
MSO4(s) + aq Mg2+(aq)+ SO42-(aq) Hsol More exothermic the enthalpy of solution, salt is more soluble

Hsol = -LE +Hhyd 2 steps rx : 1. Dissociation of lattice (-lattice energy) 2. Hydration of ions (enthalpy of hydration) Down the grp, LE & Hhyd decreases as size of cations increases

For large anions, like sulphates When moving down the group, the decrease in size of the cation does not cause a significant change of LE. However, Hhyd become less negative and has a significant change Hsol become less exothermic/negative @ more positive the solubility of sulphates decreases down the group.

SO42-

SO42-

MgSO4

SrSO4

Anomalous Properties of Beryllium Beryllium is the first element in group 2, hence it has atypical group 2 properties compare to other group 2 elements. Example: Beryllium normally forms covalent compounds where others forms ionic compound.

Beryllium oxide and hydroxide are amphoteric, while others are basic.
Beryllium can form complex ions such as [BeF4]2- while the rest does not.

The difference arise because beryllium atom is very small and has least screening effect, thus has an extremely high I.E.
Besides the high charge density, the ions enable to polarise the electron clouds of neighbouring anions.

Diagonal relationships in the periodic table :-

Certain pairs of diagonally adjacent elmts in P2 & P3 with similar chemical props

 Similarities

arise same EN & their ions have similar charge densities. Going across period : atomic radius decreases, EN increases. Going down group : atomic radius increases, EN decreases. Hence, from Be to Al, effects cancel out one another

Similarities btwn Be & Al BeO & Be(OH)2 are amphoteric Al2O3 & Al(OH)3 also amphoteric

Their oxides :

coatings are impervious to water,

extremely hard with high melting points.

Both form oxoanions in strong base: beryllate, Be(OH)42- and aluminate, Al(OH)4-. All Be & some Al compounds have significant covalent character. Beryllium chloride & aluminium chloride are covalent compounds sublime upon heating Form complexes Aq salts of Be & Al are acidic

Uses of group 2 elements and their compounds

Magnesium is used in the extraction of titanium & manufacture of alloys. Magnesium oxide used as refractory bricks as it has a higher melting point and chemical inertness. Mg(OH)2 used in antacid indigestion powder to neutralise excess stomach acid Magnesium sulphate is used as a laxative. Calcium sulphate is used as plaster of Paris (a type of building material). Lime (calcium hydroxide) is used to neutralise the acidity in soils. Calcium Carbonate is a constituent of cement & use directly as building & road foundation material. Barium sulphate is used as an instrument in the X-ray of the stomach. Barium carbonate used in rat poison.