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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

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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

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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
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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


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40.1 Characteristic Properties of the s-Block Elements


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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

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Group I elements:
Lithium Sodium Potassium

Rubidium

Caesium

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


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

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

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

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Beryllium

Group II elements:
Magnesium

Calcium

Strontium

Barium

Radium

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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

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Variation in Physical Properties


Atomic Radius and Ionic Radius (notes p. 1)

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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

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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

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

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

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

Ionization Enthalpy (notes p. 2)

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

Variations in the 1st, 2nd and 3rd ionization enthalpies of Group II elements
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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.

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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.
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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.


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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

Group I element

Electronegativity

Group II element

Electronegativity

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Li Na K Rb Cs Fr

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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

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

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

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Flame Test

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

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Flame colours

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

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

Melting Point (notes p. 4)


Variations in melting points of Groups I and II elements

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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

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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

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

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

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Extraction of sodium (not in syllabus)

Downs Cell
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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


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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

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Flowing mercury cell

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Q. 1b; Q.8

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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
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M+

Variations in hydration enthalpy of Groups I and II elements


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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
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CaSO4.2H2O CaCl2.6H2O SrSO BaCl 4 Kong A-Level Book 2.2H2O New Way Chemistry for Hong 4

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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

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Lattice Enthalpies of Group I Halides (p.10)

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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
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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.
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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

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K+H2O

Rb+H2O

Cs+H2O

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

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Strontium + water

Barium + water

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40.1 Characteristic Properties of the s-Block Elements (SB p.41, notes p. 14)

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

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

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

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

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)

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41.2 Characteristic Properties of the s-Block Elements (SB p.45)

Group I element
Li Na K Rb Cs

Monoxide
Li2O Na2O K2O Rb2O Cs2O

Peroxide
Na2O2 K2O2 Rb2O2 Cs2O2

Superoxide
KO2 RbO2 CsO2

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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


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41.2 Characteristic Properties of the s-Block Elements (SB p.46, notes p. 14)

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)

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Strontium + air

Barium + air

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

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

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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)


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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


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


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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)
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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)

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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

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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

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40.3 Variation in Properties of the compounds of the s-Block Elements (p.61)

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

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40.3 Variation in Properties of the compounds of the s-Block Elements (p.61)

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+
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O O C O

MgO

CO2
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40.3 Variation in Properties of the compounds of the s-Block Elements (p.62)

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


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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.

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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.
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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)

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Dissolution of NaCl

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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.
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Effect of charge and size of ions on Hhyd and Hlattice

Z Z H lattice + r +r

1 1 H hy d + + r r

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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

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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?
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40.3 Variation in Properties of the compounds of the s-Block Elements (p.23)

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

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Do Q. 6, 10 and Q. 7 on p. 74

The END

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