S Block Elements

40
The s-Block Elements

Characteristic Properties of the s-Block Elements Variation in Properties of the s-Block Elements Variation in Properties of the Compounds of the s-Block Elements
40.1 40.2 40.3
New Way Chemistry for Hong Kong A-Level Book 4
The Syllabus
8.1 Characteristic Properties Metallic character Low electronegativity Formation of basic oxides and hydroxides Fixed Oxidation state in their compounds Weak tendency to form complexes Flame colours of salts flame test
The Syllabus
8.2 Variation in properties of the s-block elements and their compounds
Variations in atomic radii, ionisation enthalpies, hydration enthalpies and melting points. Interpretation of these variations in terms of structure and bonding. Reactions of the elements with oxygen and water. Reactions of the oxides with water, dilute acids and dilute alkalis. Relative thermal stability of the carbonates and hydroxides. Relative solubility of the sulphates(VI) and hydroxides
3 New Way Chemistry for Hong Kong A-Level Book 4
3
Notes p. 1 s-Block elements:
Consists of Group IA and Group IIA elements

Outermost electron shell: ns1 ns2 Highly reactive metals Good reducing agents
Fixed oxidation states +1 for Group I elements +2 for Group II elements

4
40.1 Characteristic Properties of the s-Block Elements

5
40.1 Characteristic Properties of the s-Block Elements (SB p.38)
Metallic Character (not mentioned in notes)

Group I elements: Silvery in colour, tarnish rapidly in air keep immersed under paraffin oil or in vacuum sealed tubes
Soft, low boiling and melting points

Low density
weak metallic bond due to only 1 e is contributed to form bonds body-centred cubic structure -- have more spaces
Cutting Rubidium
Group I elements:
Lithium Sodium Potassium
Rubidium
Caesium

Some information about Group I elements Atomic Ionic Group radius radius I metal (nm) (nm) Li Na K Rb Cs Fr 0.152 0.186 0.231 0.244 0.262 0.270 0.060 0.095 0.133 0.148 0.169 0.176 Crystal structure b b b b b Melting Boiling point point (C) (C) 180.5 97.8 63.7 39.1 28.4 27 1330 890 774 688 690 680 Density Abundance (g cm3) on earth (%) 0.53 0.97 0.86 1.53 1.87 0.0020 2.36 2.09 0.009 0 0.000 10 Trace
b denotes body-centred cubic structure
Group II elements: silvery in colour harder and higher boiling and melting points than Group I counterparts stronger metallic bond due to 2e are contributed to form bond and smaller atomic sizes show different crystal structures
Beryllium
Group II elements:
Magnesium
Calcium
Strontium
Barium
Radium
10
10
40.1 Characteristic Properties of the s-Block Elements (SB p.39) Some information about Group II elements Atomic Ionic Melting Group Crystal radius radius point II metal structure (nm) (nm) (C) Be Mg Ca Sr Ba Ra 0.112 0.160 0.197 0.215 0.217 0.220 0.031 0.065 0.099 0.113 0.135 0.140 h h f f b 1278 648.8 839 769 729 697 Boiling point (C) 2477 1100 1480 1380 1640 1140 Density Abundance (g cm3) on earth (%) 1.85 1.75 1.55 2.54 3.60 5.0 0.000 28 2.33 4.15 0.038 0.042 Trace
h, f and b denote hexagonal close-packed, face-centred cubic and body-centred cubic structures respectively
11
11
Variation in Physical Properties

Atomic Radius and Ionic Radius (notes p. 1)
12
12
41.3 Variation in Properties of the s-Block Elements (SB p.52)
Question:
The atomic and ionic radii increase down the Groups, why? outermost shell electrons become further away, and more inner shells shielding the outermost shell electrons
attraction between the nucleus and the outermost shell

electrons decreases atomic and ionic radii increase
13
13
Question:
Atomic and ionic radii decrease when going from
Group I to II in each period, why?

Group II elements have 1 more proton and electron than Group I elements. Increase in nuclear charge outweighs
the increase in shielding effect of additional electron of the

same shell. atomic and ionic radii decrease
14
14
Question:
Ionic radius of any Group I or II element is smaller than the atomic radius, why? after losing the outermost shell electron(s), there is one electron shell less in the cation than in the atom. Increase in p/e ratio
15
15
Ionization Enthalpy (notes p. 2)
16
16
Variations in the 1st, 2nd and 3rd ionization enthalpies of Group II elements
17
1st I.E. is much smaller than 2nd I.E. for Gp. I elements
For the 1st I.E., electron is further away from the nucleus and shielding effect of inner shell electrons small 1st I.E. For 2nd I.E., electron is removed from stable noble gas configuration and higher effective nuclear charge large 2nd I.E.
18
18
The ionization enthalpies decrease down the Groups

Reason: atomic sizes increase down the group
the outermost shell electron(s) is/are further away from

the nucleus, they will be better shielded by inner electron shells.
less attractive force experienced

less energy is required to remove the electrons
Because of the high I.E., Li and Be forms a few covalent compounds

instead of forming Li+ and Be2+ respectively.
19
40.1 Characteristic Properties of the s-Block Elements (SB p.41, notes p. 3))
Low Electronegativity 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.

20
20
Group II elements are relatively more electronegative than Group I counterparts
higher nuclear charge, stronger attraction to outermost shell electrons
Group I element
Electronegativity
Group II element
Electronegativity
21
Li Na K Rb Cs Fr
1.0 0.9 0.8 0.8 0.7
Be Mg Ca Sr Ba Ra
1.5 1.2 1.0 1.0 0.9
21
Characteristic Flame Colours of Salts The outermost shell electrons of Group I & II elements are weakly held The electrons can be excited to higher energy levels on heating When electrons return to ground state, radiations are emitted The radiations fall into the visible light region The flame colour is a characteristic property of the element
22
22
Flame Test
23
23
24
24
Flame colours
25
25
Weak tendency to form complexes (not mentioned in notes) Complex: Polyatomic ion or neutral molecule formed when molecular or ionic gropups (called ligands) form dative covalent bonds with a central ion.
Group I & II elements seldom form complex: - s-block ions do not have low energy vacant orbitals available for dative covalent bonds. - Low ionic charge
26
Melting Point (notes p. 4)

Variations in melting points of Groups I and II elements
27
27
Observations:
melting point decreases as going down Groups I and II Reason: the ionic size of the elements increases attraction between ions and electrons becomes weaker metallic bond is weaker
28
28
Observations:
melting points of Group II elements are much higher than those of Group I elements Reason: no. of valence electrons per mole contributed to the delocalized electron sea is greater. Group II elements have higher ionic charge the attractive force between ions and electrons are stronger metallic bond is stronger
29
29
Observations:
irregularity in the general decrease in melting point down Group II elements Reason: 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
30
30
Extraction of sodium (not in syllabus)
Downs Cell
31
Manufacture of sodium hydroxide

graphite anodes chlorine
+
used brine saturated brine
mercury alloyed with sodium flow of mercury flowing mercury (as cathode)
Water
Mercury (recycle)
Flowing mercury cell

32
During electrolysis, chlorine is liberated at the anode and sodium at the cathode. At anode (graphite): 2Cl (aq) Cl2(g) + 2e-
At cathode (mercury): Na+(aq) + e- Na(s);
Na(s) + Hg(l) Na/Hg(l)

sodium amalgam
33
33
Flowing mercury cell
34
Q. 1b; Q.8
34
40.3 Variation in Properties of the s-Block Elements (SB p.56, notes p. 8)
Hydration Enthalpy
Xn+(g) + aq Xn+(aq)
Hydration enthalpy (Hhyd) is the amount of energy released when one mole of aqueous ions is formed from its gaseous ions.
Hhyd must be negative value. Hhyd depends on charge density charge/size Higher the charge, stronger the attraction, more energy released Smaller the size, stronger the attraction, more energy released
35
35
M+
Variations in hydration enthalpy of Groups I and II elements

36
magnitude of hydration enthalpies become smaller (less negative) as going down the Groups Reason: the ionic size of the elements increases down the group, the charge density decreases the attractive force between water molecules and ions
becomes weaker
the hydration enthalpy becomes less negative Down the group, fewer molecules of water of
crystallization
Na2CO3.10H2O MgSO4.7H2O MgCl2.6H2O K2CO3.2H2O
37
CaSO4.2H2O CaCl2.6H2O SrSO BaCl 4 Kong A-Level Book 2.2H2O New Way Chemistry for Hong 4
37
Observations:
hydration enthalpies of Group II ions are more negative
than those of Group I ions

Reason: Group II ions have higher charge and smaller size
charge density is much higher that of Group I ions

the attractive force would be much stronger
38
38
Lattice Enthalpies of Group I Halides (p.10)
39
39
Lattice Enthalpies of Group I Halides (p.10)

Good agreement between calculated and measured value. Why? Lattice Enthalpies decrease down the group: Reasons: Size increase Internuclear distance increase Attractive force between opposite ions decrease
40
Lattice Enthalpies of Group II Halides (p.11)

Discrepancies occurred between calculated and measured values. Reason: Covalent characters occurred in small cations. Group II Halides have a higher lattice enthalpies than Group I Halides. Reason: Higher charge; smaller size.
41
40.1 Characteristic Properties of the s-Block Elements (SB p.43, notes p. 13)
Formation of Hydroxides reactions with water
All Group I metals react with H2O to form metal hydroxides and H2 gas
e.g. 2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
2K(s) + 2H2O(l) 2KOH(aq) + H2(g)
Li+H2O
Na +H2O
42
42
K+H2O
Rb+H2O
Cs+H2O
43
43
All Group II metals (except Be) react with H2O to form metal hydroxides and H2 gas (Mg reacts with hot water). e.g. Ca(s) + 2H2O(l) Ca(OH)2(aq) + H2(g) Sr(s) + 2H2O(l) Sr(OH)2(aq) + H2(g)
Be does not react with H2O(l or g)
44
44
Strontium + water
Barium + water
45
45
Formation of Basic Oxides

Group I elements
Produce more than one type of oxides (except Li) All are ionic Three types of oxides: normal oxides (monoxides), peroxides, superoxides Relationship between three oxides: O2 O2
1 O2 2
2
O O
2O2
superoxide
O2
monoxide
peroxide
46
46
Li forms the monoxide only 4Li(s) + O2(g) 2Li2O(s)

180C
Na forms the monoxide and peroxide when O2 is abundant

4Na(s) + O2(g) 2Na2O(s)
300C 2Na2O(s) + O2(g) 2Na2O2(s)
180C
47
47
K forms the monoxide, peroxide and superoxide

180C 4K(s) + O2(g) 2K2O(s) 300C 2K2O(s) + O2(g) 2K2O2(s)
K2O2(s) + O2(g) 2KO2(s)
3000C
Rb, Cs also forms superoxides

3000C Rb2O2(s) + O2(g) 2RbO2(s) C Cs2O2(s) + O2(g) 3000 2CsO2(s)
48
48
Group I element
Li Na K Rb Cs
Monoxide
Li2O Na2O K2O Rb2O Cs2O
Peroxide
Na2O2 K2O2 Rb2O2 Cs2O2
Superoxide
KO2 RbO2 CsO2
49
49
40.1 Characteristic Properties of the s-Block Elements (SB p.42 notes p. 14)
Li does not form peroxides or superoxides
Reason: Li+ is small high polarizing power serious distortion on electron cloud of peroxide or superoxide (large polyatomic anions)
more distortion , more unstable

Li2O2 and LiO2 do not exist
K+, Rb+ and Cs+ ions are large
Low polarizing power peroxides and superoxides are relatively stable

50
Group II Elements
Form normal oxides only, except Sr, Ba which can form peroxides. All are basic (except BeO which is amphoteric), why? 2Be(s) + O2(g) 2BeO(s) 2Mg(s) + O2(g) 2MgO(s) 2Ca(s) + O2(g) 2CaO(s) 2Ba(s) + O2(g) 2BaO(s)
2BaO(s) + O2(g)
2BaO2(s)
51
51
Strontium + air
Barium + air
52
52
Group II element Be Mg Ca Sr Ba Reason:
Normal oxide BeO MgO CaO SrO BaO
Peroxide SrO2 BaO2
Superoxide
Be, Mg, Ca peroxide do not exist, why?

High charge density high polarizing power
serious distortion on electron cloud of the peroxide ion
53
53
40.3 Variation in Properties of the compounds of the s-Block Elements ( p.59) notes p. 14 2(e)
Reactions of Oxides of s-Block Elements

Reaction with Water
Group I oxides react with H2O to form hydroxides

Normal oxides: e.g. Li2O(s) + H2O(l) 2LiOH(aq) Peroxides: e.g. Na2O2(s) + 2H2O(l) 2NaOH(aq) + H2O2(aq)
Dissolution of Na2O2 in H2O containing phenolphthalein
Superoxides: e.g. 2KO2(s) + 2H2O(l) 2KOH(aq) + H2O2(aq) + O2(g)

54
54
Group II oxides (except BeO, MgO) react with H2O to form a weakly alkaline solution e.g. CaO(s) + H2O(l) Ca(OH)2(aq) (weakly alkaline)
The basicity of all Group II oxides increases down the group BeO is amphoteric BeO(s) + 2H+(aq) Be2+(aq) + H2O(l)
hot
BeO(s) + 2OH(aq) + H2O(l) [Be(OH)4]2(aq)

hot
MgO is slightly soluble in water, but dissolves in acids to form salts

55
BaO2(s) + 2H2O(l) Ba(OH)2(aq) + H2O2(aq)

55
40.3
Variation in Properties of the compounds of the s-Block Elements (p.60, not mentioned in notes)
Reaction with Acids
All oxides of s-Block elements are basic except BeO which is amphoteric
Normal oxides: e.g. CaO(s) + 2HCl(aq) CaCl2(aq) + H2O(l) Peroxides: e.g. Na2O2(s) + 2HCl(aq) 2NaCl(aq) + H2O2(aq) Superoxides: e.g. 2KO2(s) + 2HCl(aq) 2KCl(aq) + H2O2(aq) + O2(g)
56
56
40.3 Variation in Properties of the compounds of the s-Block Elements (p.60)
Reaction with Alkalis
No reaction between the oxides of s-block elements with

alkalis except BeO
BeO is amphoteric, it reacts with NaOH to give

Na2Be(OH)4 BeO(s) + 2NaOH(aq) + H2O(l) Na2Be(OH)4(aq)
57
57
40.3 Variation in Properties of the compounds of the s-Block Elements (p.60) notes p. 15, 18
Relative Thermal Stability of the Carbonates and Hydroxides
Thermal stability refers to the resistance of a compound to decomposition on heating

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) charges &
(2) sizes of ions
58
58
40.3 Variation in Properties of the compounds of the s-Block Elements (p.61) notes p. 18
Compound with large polarizable polyatomic anion (large electron cloud, as shown in notes), the thermal stability depends on the polarizing power (charge density) of cations The stronger the polarizing power, the electron cloud of anion will be distorted to greater extent The compound tends to be less thermal stable
59
59
Group II carbonates/hydroxides are less stable than Group I Group II ions are smaller and have a higher charge than Group I ions in the same period Greater polarizing power The carbonates and hydroxides of Group II metals are less stable on heating e.g. K2CO3 is stable upon heating while CaCO3 decomposes on heating
60
60
Most carbonates and hydroxides of Group II metals readily undergo decomposition on heating to give oxides (more stable) e.g. MgCO3(s) MgO(s) + CO2(g) Ca(OH)2(s) CaO(s) + H2O(g)
2+
O H MgO
+
Mg
O H
H2O
Mg2+
61
O O C O
MgO
CO2
61
Down the group, the size of cations increases polarizing power decreases compound with large anion become more stable thermal stability of carbonates & hydroxides of Groups I and II metals increases down the group
Do Q. 2b on p. 73
Effect of sizes of cations on thermal stability of compounds

62
Q.
Explain briefly why lithium hydrogencarbonate does not exist as a solid while other Group I hydrogencarbonates can be found in solid state.
In solid form, the cation and anion are close to each other. Due to small size of Li+, it has a high polarizing power. This distorts the electron cloud of HCO3-, making the anion unstable. As the size of cations increases down the group, the polarizing power decreases, therefore, solid hydrogencarbonates can be formed.
A.
63
63
Effect of Heat on s-block carbonates and hydroxides (p.19)

i. Carbonates
Group I:
Group II:
All are thermally stable except Lithium.

All decompose on heating forming metal oxides and carbon dioxide.
ii. Hydroxides (p.21) Group I: Group II: All are thermally stable except Lithium. All decompose on heating forming metal oxides and water.
64
64
40.3 Variation in Properties of the compounds of the s-Block Elements (p.63) notes p. 21
Relative Solubility of the Sulphates(VI) and Hydroxides

Processes involved in Dissolution and their Energetics
When an ionic solid is dissolved in water, two processes are taken place: 1. Breakdown of the ionic solid (-ve lattice enthalpy) 2. Stabilization of ions by water molecules (hydration enthalpy released)
65
65
Dissolution of NaCl
66
66
Solubility of s-block Sulphates and Hydroxides (p.23)

MX(s) Hs M+(aq) + X-(aq)
-U
Hhyd
M+(g) + X-(g)
A low modulus of lattice enthalpy and a high modulus of hydration enthalpy favour the dissolving process.
67
67
Effect of charge and size of ions on Hhyd and Hlattice
Z Z H lattice + r +r
1 1 H hy d + + r r
68
68
Solubility of s-block Sulphates and Hydroxides

i. For large anions, like sulphates When moving down the group, the decrease in size of the cation does not cause a significant change of U. However, Hhyd become less negative and has a significant change the solubility of sulphates decreases down the group.
SO42-
SO42-
MgSO4
69
SrSO4
69
ii. For smaller anions, like hydroxides When moving down the group, the increase in size of the cation causes a significant change of U but Hhyd change a little because of the great hydration energy of the anion. Therefore the solubility of hydroxide increases down the group.
Mg(OH)2
iii.
70
Sr(OH)2
Group I sulphates and hydroxides are more soluble than that of Group II. Why?
70
Relative Solubility of the Sulphates(VI) and Hydroxides Trend and Interpretation
The sulphates(VI) and hydroxides of Group I metals are

more soluble in water than those of Group II metals
Group I metals has a smaller charge and larger size than Group II metals in the same period The lattice enthalpies of Group I compounds are smaller in magnitude than those of Group II compounds The enthalpy changes of solution are more ve
71
71
Do Q. 6, 10 and Q. 7 on p. 74
The END
72
72

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40

The s-Block Elements

40.1 40.2 40.3

New Way Chemistry for Hong Kong A-Level Book 4

New Way Chemistry for Hong Kong A-Level Book 4

Notes p. 1 s-Block elements:

Consists of Group IA and Group IIA elements

Fixed oxidation states +1 for Group I elements +2 for Group II elements

40.1 Characteristic Properties of the s-Block Elements

40.1 Characteristic Properties of the s-Block Elements (SB p.38)

Metallic Character (not mentioned in notes)

Soft, low boiling and melting points

New Way Chemistry for Hong Kong A-Level Book 4

New Way Chemistry for Hong Kong A-Level Book 4

40.1 Characteristic Properties of the s-Block Elements (SB p.39)

b denotes body-centred cubic structure

New Way Chemistry for Hong Kong A-Level Book 4

40.1 Characteristic Properties of the s-Block Elements (SB p.39)

New Way Chemistry for Hong Kong A-Level Book 4

New Way Chemistry for Hong Kong A-Level Book 4

New Way Chemistry for Hong Kong A-Level Book 4

Variation in Physical Properties

New Way Chemistry for Hong Kong A-Level Book 4

41.3 Variation in Properties of the s-Block Elements (SB p.52)

attraction between the nucleus and the outermost shell

New Way Chemistry for Hong Kong A-Level Book 4

Group I to II in each period, why?

the increase in shielding effect of additional electron of the

New Way Chemistry for Hong Kong A-Level Book 4

41.3 Variation in Properties of the s-Block Elements (SB p.52)

New Way Chemistry for Hong Kong A-Level Book 4

41.3 Variation in Properties of the s-Block Elements (SB p.53)

Ionization Enthalpy (notes p. 2)

New Way Chemistry for Hong Kong A-Level Book 4

41.3 Variation in Properties of the s-Block Elements (SB p.54)

New Way Chemistry for Hong Kong A-Level Book 4

The ionization enthalpies decrease down the Groups

the outermost shell electron(s) is/are further away from

less attractive force experienced

Because of the high I.E., Li and Be forms a few covalent compounds

Low Electronegativity All have low electronegativity values

the outermost electron shell is effectively shielded by inner electron shells.

- increase in shielding effect.

New Way Chemistry for Hong Kong A-Level Book 4

40.1 Characteristic Properties of the s-Block Elements (SB p.41)

Group II elements are relatively more electronegative than Group I counterparts

higher nuclear charge, stronger attraction to outermost shell electrons

New Way Chemistry for Hong Kong A-Level Book 4

1.0 0.9 0.8 0.8 0.7

1.5 1.2 1.0 1.0 0.9

40.1 Characteristic Properties of the s-Block Elements (SB p.43)

New Way Chemistry for Hong Kong A-Level Book 4

New Way Chemistry for Hong Kong A-Level Book 4

40.1 Characteristic Properties of the s-Block Elements (SB p.43)

New Way Chemistry for Hong Kong A-Level Book 4

New Way Chemistry for Hong Kong A-Level Book 4

40.1 Characteristic Properties of the s-Block Elements (SB p.43)

41.3 Variation in Properties of the s-Block Elements (SB p.55)

Melting Point (notes p. 4)

New Way Chemistry for Hong Kong A-Level Book 4

New Way Chemistry for Hong Kong A-Level Book 4

New Way Chemistry for Hong Kong A-Level Book 4

41.3 Variation in Properties of the s-Block Elements (SB p.56)