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The s-Block Elements

Introduction The s-block elements refer to the elements in group I (alkali metals) and II (alkaline earth metals). The meaning of s-block is that their outermost shell electrons are in s-orbitals. e.g. Li: [He]2S1 Na: K: Be: [He]2S2 Mg: Ca:

Characteristic properties of the s-block elements 1. Metallic character and low electronegativity The s-block elements all have the properties of metals. They form metallic bonds. Because they lose their outermost shell electrons very easily, they have very low electronegativities (very electropositive). 2. Formation of basic oxides and hydroxides The oxides of s-block elements are highly basic. Na2 O(s) + H2 O(l) --- 2 NaOH(aq) 2 Na2 O2 (s) + 2 H2 O(l) --- 4 NaOH(aq) + O2 (g) K2O(s) + 2 HCl(aq) --- 2 KCl(aq) + H2 O(l) 3. Predominantly ionic bonding with fixed oxidation state in their compounds. The oxidation state of group I metals are all +1 The oxidation state of group II metals are all +2 This fact can be explained in terms of energetic terms.

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4. Characteristic flame colours of salts.

The flame test is very useful in qualitative analysis for us to determine the unknown metal ion (cations) 5. Weak tendency to form complex A complex is a polyatomic ion or neutral molecule formed when moleculat group or ionic groups (called ligands) form dative covalent bonds with a central metal atom or cation.

The formation of complexes required the presence of vacant low- lying d-orbitals which is available for the transition metals (d-block elements). But for s-block metals, this is not available. Hence s-block elements seldom form complexes.

Variation in properties of the s-block elements and their compounds 1. Atomic radii and ionic radii

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Trend: There is a general increase in atomic radii and ionic radii down the group. Reason: Down the group, there is increase in number of quantum shells. Trend: Going from group I to II, in the same period, the atomic and ionic radii decrease. Reason: As there is increase in effective nuclear charge from group I to II, the attraction between nucleus and the electrons increases. Trend: The ionic radii of any element is smaller than its atomic radii. Reason: Since the elements form cation by losing electron(s), there is one electron shell less in the cation than the atom.

2. Ionization enthalpies (energies)

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Trend: For group I and II elements, the I.E decreases down the group. Reason: Down the group, the atomic radius increases due the increase in number of quantum shells. Hence the outer electrons are less strongly held. Trend: For group I and II elements, the successive I.E. increases. Reason: There is increase in effective nuclear charge after one electron is removed. Hence the remaining electrons should be more difficult to be removed. Trend: There is a sharp increase in the 2nd I.E of group I elements and the 3rd I.E of group II elements Reason: The second electron of group I elements and the third electron of group II elements are removed from an inner shell.

3. Hydration enthalpies (energies) Trend: Down group I and II, the hydration enthalpies of the cations decrease. Reason: Down both group, the cations get larger due to the Increase in number of quantum shells. Hence the charge density decreases and the electrostatic interaction between polar water molecules and cations becomes less. Trend: Group II cations have hydration enthalpies higher than the group I cations in the same period. Reason: Group II cations have a double positive charge +2 While group I cations have only +1 charge. Hence group II cations have a higher charge density and a higher hydration enthalpy.

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4. Melting points

Trend: The melting points of group I and II metals decrease down the group. Reason: Down the group, the ionic radii of metallic ions increase. This decreases the charge density of +1 or +2 ions and the electrostatic attraction between the positive metallic ions and the delocalized electrons decrease. This results in the decrease in strength of metallic bonds. Trend: The melting points of group II metals are much higher than the corresponding group I metals in the same period. Reason: The ions of group II have a higher positive +2 charge while the group I ion is +1. Hence group II metallic ions have higher charge density. Moreover, group II metals give two delocalized electrons per atom while group I metals only give one. This result in the stronger metallic bond for group II metals. Also the packing of crystal structure has effect on the melting points.

All group I metals have the structure of body-centred cubic (b.c.c.) which is not a close packing. For group II metals, most have close packing of hexagonal closed packing (h.c.p.) or cubic close packing (c.c.p.). Hence group II metals usually have a higher melting point.

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Reactions of the metals 1) with hydrogen s-block metals react with hydrogen to form hydrides. 2 Na(s) + H2 (g) --- 2 NaH(s) Ca(s) + H2 (g) --- CaH2 (s) Most of the hydrides are ionic. Hydrides react with water to form hydrogen gas and An alkaline solution. 2) with oxygen s-block metals react with oxygen to form oxides. Superoxides O2 - (K, Rb, Cs burn in oxygen) K(s) + O2 (g) --- KO2 (s) Peroxides O2 2- (Na, Baburn in oxygen) 2 Na(s) + O2 (g) --- Na2O2 (s) (Normal) oxides O2- (Li and group II metals burn in oxygen) 4 Na(s) + O2 (g) --- 2 Na2O(s) 2 Ca(s) + O2 (g) --- 2 CaO(s) 3) with chlorine s-block metals combine directly with chlorine to form chlorides. 2 Na(s) + Cl2 (g) --- 2 NaCl(s) Ca(s) + Cl2 (g) --- CaCl2 (s) 4) with water Most s-block metals react water to form hydroxides and hydrogen. 2 Na(s) + 2 H2 O(l) --- 2 NaOH(aq) + H2 (g) Ca(s) + 2 H2 O(l) --- Ca(OH)2 (aq) + H2 (g)

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Reactions of the oxides 1) with water Most group I and II oxides react with water to form hydroxides. Li2 O(s) + H2 O(l) --- 2 LiOH(s) Na2 O2 (s) + 2 H2 O(l) --- 2 NaOH(aq) + H2 O2 (aq) 2 KO2 (s) + 2H2 O(l) --- 2 KOH(aq) + H2 O2 (aq) + O2 (g) CaO(s) + H2 O(l) --- Ca(OH)2 (aq)

2) with acids and alkalis All the oxides of s-block elements are basic. Na2 O(s) + 2 H+(aq) --- 2 Na+(aq) + H2 O(l) MgO(s) + 2 H+ (aq) --- Mg2+(aq) + H2 O(l)

BeO(s) is amphoteric, BeO(s) + 2 H+(aq) --- Be2+(aq) + H2 O(l) BeO(s) + 2 OH-(aq) + H2 O(l) --- [Be(OH)4 ]2-(aq)

Reactions of the hydrides 1) with water The hydrides of group I and II metals react with water to form metal hydroxides and hydrogen. NaH(s) + H2 O(l) --- NaOH(aq) H2 (g) CaH2 (s) + 2 H2 O(l) --- Ca(OH)2 (aq) + 2 H2 (g)

Reactions of the chlorides 1) with water The chlorides of group I and II metals are mainly ionic. They simply dissolve in water. NaCl(s) + H2 O(l) --- NaCl(aq) BeCl2 (s) + H2 O(l) --- BeO(s) + 2 HCl(aq)

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Relative stability of the carbonates For group I carbonates, Li2 CO3 (s) --- Li2 O(s) + CO2 (g) G Na2 CO3 , K2 CO3 , Rb2 CO3 , Cs2 CO3 do not decompose on heating. All group II carbonates decompose on heating to give the oxides and carbon dioxide. MgCO3 (s) --- MgO(s) + CO2 (g) G BaCO3 () --- BaO(s) + CO2 (g) G General trends: 1. Carbonates of I metals are more stable (thermally) than those of group II. 2. Thermal stability increases on going down both groups. 3. Lithium carbonate is the only one that decomposes on heating in group I. Explanation: The group II metal ions have smaller size than those of group I metal ions and have a higher charge. Hence the charge density of group II metal ions is higher and their polarizing power is greater. This distorts the electron cloud of the carbonate ion to a greater extent. Hence group II carbonates have a higher covalent character than group I carbonates and they will be decomposed more readily on heating. On the same group, the size of metal ions increases down the group. The charge density decreases and the polarizing power decreases also. The distortion of electron cloud of carbonate ion decreases and the ionic character increases. Hence they will be decomposed less readily on heating down the group.

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Relative solubility of the sulphates(VI) and hydroxides The energy cycle for a compound to dissolve in water is as follows:

If G solution is ve , the compound will generally be soluble. H If G solution is +ve , the compound will generally be insoluble. H From the above energy cycle, G solution =G hydration - G lattice H H H

Trends: 1. The solubility of the hydroxide increases down both group I and II. 2. The solubility of the sulphates decreases down both group I and II. Explanation: For the sulphate(VI), the cations are much smaller than the anions. Down the group, the increase in size of the cations does not cause a significant decrease inG lattice (G lattice is determined by H H
1 ). Hence the decrease inGHhydration is more significant. As a result, theGHsolution become r +r
+

less negative (exothermic) and the solubility decreases. For the hydroxides, the sizes of the anions and cations are of the same order. Down the group, the G lattice decreases significantly but the decrease in G hydration relatively small. Hence GHsolution H H become more negative (exothermic) and the solubility increases. Uses of the compounds of the s-block elements 1. Sodium carbonate is used in the manufacture of glass. 2. Sodium hydrogencarbonate is used in baking powder. 3. Magnesium hydroxide is used as an antacid. 4. Slaked lime is used in neutralization of acids in industrial effluents. 5. Strontium compounds are used in fireworks.