Periodicity - Suggested Solutions

Topic 9.1: Periodicity

AJC/2009/P2/Q1a,b 1

CJC/2009/P2/Q1a-d 2(a)(i) Mg+(g) Mg2+(g) + e(ii) The second ionisation involves removal of an electron from the 3p subshell from Si+, and the 3s subshell from Al+. Since the 3p subshell is on average further from the nucleus / at a higher energy level / experiences more shielding than the 3s subshell, the electron removed from Si+ is less tightly held and requires less energy to remove. Neon, being already in the gaseous state, is ionised first and emits light, whereas sodium is in the solid state and takes time to vaporise before it can be ionised. OR Neon has a higher first ionisation energy than sodium. The initial power surge when the light is turned on is able to ionize neon, giving rise to the red light, after which the power drops and is only enough to ionise sodium, giving rise to the orange light.

(b)

(c)(i) Al2O3 has a giant ionic lattice structure with strong ionic bonds / high lattice energy / partial covalent character, hence it is insoluble.
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SiO2 has a giant molecular structure with strong covalent bonds requiring large amounts of energy to break, hence it is insoluble. (ii) AlCl3 dissolves to give [Al(H2O)6]3+(aq) which undergoes hydrolysis due to the high charge density on Al3+: [Al(H2O)6]3+ [Al(H2O)5(OH)]2+ + H+ OR 2AlCl3 + 6H2O Al2O3 + 6HCl OR AlCl3 + 3H2O Al(OH)3 + 3HCl SiCl4 hydrolyses in water to give HCl, a strong acid / H+ is produced: SiCl4 + 2H2O SiO2 + 4HCl OR SiCl4 + 4H2O Si(OH)4 + 4HCl (d)(i) Solubility of Li2O is lower than that of BaO. Therefore, the basicity of Li2O is also lower than that of BaO. (ii) Percentage change in mass =
[2(6.9) + 12.0 + 3(16.0)] [2(6.9) + 2(16.0)] 100 % [2(6.9) + 2(16.0)]

= 61.1%

DHS/2009/P2/Q1a 3 (i) pH of chloride

Na (ii)

Mg

Al

Si

The pH is 3. Aluminium chloride undergoes hydrolysis to give an acidic solution due to the high polarising power of Al3+. Silicon chloride:

(iii)

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Periodicity - Suggested Solutions

SiCl4 (l) + 2H2O (l)

SiO2 (s) + 4HCl (aq)

Phosphorus pentachloride: PCl5 (l) + 4H2O (l) HCI/2009/P3/Q3a 4 Melting

point /oC

H3PO4 (aq) + 5HCl (aq)

M.p. /oC

Na

Mg

Al

Si

S Si

Cl

Ar

High melting point from Na to Al as they exist as giant metallic structures with strong metallic bonds of increasing strengths due to smaller cationic radius and increased number of delocalized electrons. Very high melting point for Si as it exists as a giant covalent structure with an extensive network of strong covalent bonds. These strong bonds require a lot of energy to break before melting can occur. Low melting point from P to Ar as they exist as simple molecular structures, consisting of discrete molecules with weak dispersions forces between the molecules. Melting point decreases from S8 > P4 > Cl2 > Ar because the size of the electron clouds decreases from S8 > P4 > Cl2 > Ar, such that dispersion forces are weaker. IJC/2009/P2/Q2a 5 When a mixture of silicon dioxide and carbon is heated in a stream of chlorine, silicon tetrachloride and carbon monoxide are formed. (i)

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(ii)

(iii) 1. 2.

Silicon dioxide and silicon tetrachloride each behaves differently when added to water.

IJC/2009/P3/Q4b 6

JJC/2009/P2/Q5a,b 7 (a) (i) X is Na/ Mg W is Si (ii) [1] [1] [1]

SiCl4 + 2H2O SiO2 + 4HCl

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Periodicity - Suggested Solutions

(b)

To 2 separate samples of the powder, add in dilute HCl and dilute NaOH respectively. If the powder dissolves in both dilute HCl and dilute NaOH to form colourless solution, it is Al2O3. If the powder dissolves only in dilute HCl to form colourless solution, it is MgO. If the powder does not dissolve in both dilute HCl and dilute NaOH, it is SiO2.

MI/2009/P2/Q3c 8 Firstly, add NaOH to the solids separately. Only Al2O3 will dissolve. Al2O3 + 2NaOH + 3H2O 2Na[Al(OH)4] Next, add HCl to the remaining solids separately. Only MgO will dissolve. MgO + 2HCl MgCl2 + H2O SiO2 remains as a solid. (1m for description of behaviour of the solids when reagents are added. 0m if either one of the observations are missing.) NJC/2009/P2/Q3a-c 2Al3+ + 3H2O 9(a) (i) Al2O3 + 6H+ 2[Al(OH)4] Al2O3 + 2OH + 3H2O (b) (i)
Ionic Radius

Na

Mg

Al

Si

Cl

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Periodicity - Suggested Solutions

pH

Na2O

MgO

Al2O3

SiO2

P4O10

SO3

(ii)

Ionic Radius: There are two isoelectronic series in period 3. Within each series, an increasing number of protons results in increasingly stronger nuclear attraction experienced by the valence electrons. Valence electrons are pulled closer to nucleus, leading to a decreasing trend in ionic radius. Anionic series has a larger size than cationic series as the valence electrons are in a higher principal quantum shell, experience weaker nuclear attraction and are less tightly held. pH: Na2O and MgO are ionic oxides that dissolve completely in water to form basic solution. Al2O3 and SiO2 are insoluble in water pH of solution is that of water. P4O10 and SO3 are covalent oxides that hydrolyse in water to give acidic solution.

(c) (i) [Mg(H2O)6]2+ + H2O NYJC/2009/P2/Q3a,b 10 (a)

[Mg(H2O)5(OH)]+ + H3O+

Aluminium(III) oxide and phosphorous(V) chloride differ in their behaviour with water. Al2O3 + H2O No reaction PCl5 + 4 H2O H3PO4 + 5 HCl [2]

(i)

(ii)

Al2O3 - very strong ionic bonds, high LE no reaction with water PCl5 - simple molecular structure, chloride is acidic hydrolysis occurs [2]

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(iii) (b)

For PCl5 - pH is 2-3

[1]

(i) SiO2 : Gp IV (non-metallic) oxide, expected to form acidic oxide and to react with base. Hence, given reaction is expected. (ii) BeO : Gp II (metallic) oxide, expected to form basic oxide and to react with acid. But given reaction is with an alkali. Hence, given reaction is not expected. [Acceptable answer]: due to high charge density of Be2+ion, Beo shows a high degree of covalency, and is amphoteric like Al2O3). Hence, BeO also shows acidic properties and would react with alkali NaOH to give a salt, Na2BeO2 and water.] [3]

PJC/2009/P2/Q1 11

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SAJC/2009/P3/Q1c 12 (c) Since the oxide of Y can react with both NaOH and HCl, it is an amphoteric oxide. Among the possible elements, only the oxide of aluminium is amphoteric in nature: Compound Y is Al. Al2O3 (s) + 6HCl (aq) 2AlCl3 (aq) + 3H2O (l) 2NaAl (OH)4 (aq) [5] [Al(H2O)6]3+ (aq) + 3Cl (aq) [Al(H2O)5(OH)]2+ (aq ) + H3O+ (aq)

Al2O3 (s) + 2NaOH (aq) + 3H2O (l) which reacts with the NaOH. AlCl3 (s) + aq [Al(H2O)6]3+ (aq) + H2O (l) oxide is insoluble in water. Compound Z is P.

In the presence of water, AlCl3 undergoes hydrolysis to form an acidic solution,

Phosphorus chloride and phosphorus oxide will react with water but silicon

PCl3(l) +3H2O(l) H3PO3 (aq)+3HCl (aq) or PCl5 (s)+ 4H2O(l) H3PO4(aq) + 4HCl (aq) P4O6 (s) + 6H2O (l) 4H3PO3 (aq) P4O10 (s) + 6H2O (l) 4H3PO4 (aq) or

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SRJC/2009/P2/Q1a-d 13(a) (i) Across the period from Na to Cl, nuclear charge increases [1/2M]; but increase in shielding effect is negligible as electron is added to the same quantum shell; [1/2M] Hence, the effective nuclear charge increases OR the electrostatic forces of attraction between the nucleus and the outermost/ valence electrons increases across the period. [1M] Therefore, the atomic radius decreases across the period from Na to Cl. Na+ has one electron less than Na or Na+ has one quantum shell less than Na. Nuclear charge remains the same. [1M] The electrostatic forces of attraction between the nucleus and the remaining electrons are greater for Na+. [1M]

(ii)

(b)(ii) The anionic radii of P3, S2 and Cl are larger than their respective atoms. This is due to electrons are being added to the same valence shell, resulting in greater interelectronic repulsions between the valence electrons. [1M] Across the period from P3, S2 and Cl, the anionic radii decrease. The nuclear charge increases across the period with negligible increase in shielding effect resulting in the corresponding increase in the effective nuclear charge OR electrostatic forces of attraction between the nucleus and the valence electrons. [1M] (c)(i) 1s22s22p63s23p4 or [Ne] 3s23p4 [1M] (ii) Sulphur is in Period 3 and hence has the availability of 3d orbitals to expand beyond its octet structure while oxygen cannot expand its octet due to the absence of dorbitals. [1M] 740,
760

(d)

1500,
6200

7700,
2800

10500,
3100

13600,

18000,

21700

4400

3700 (difference in IE)

- Element A belongs to Group II [1M] - Largest energy difference between the 2nd and 3rd IE. [1/2M] - Removal of the 3rd electron is from an inner quantum shell which requires more energy. [1/2M] Formula: ACl2 [1M]

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TPJC/2009/P2/Q1 14

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