Unit 1 Mod 3 Period 3 elements Module 3 Period 3 elements

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Variations in atomic/ionic radii, melting point and electrical conductivity of period 3 elements Atomic radii variation Moving from left to right of the period, the atomic radii decrease. On traversing the period there are 2 factors operating:- (1) the addition of electrons to the same shell and (2) the number of protons increasing by one thus increasing the effective nuclear charge. What is effective nuclear charge? This is the residual attraction of the nucleus to the outermost electrons after shielding from the inner core of electrons have taken place. By adding electrons, there is a slight repulsion between the core electrons and the newly added electron causes a slight increase in the radius, but the dominant effect is the increase in the effective nuclear charge, the positive charge attracts the negatively charged electrons causing them to be drawn inward towards the nucleus thus reducing the atomic radius.

For ionic radii, one must remember that in some cases cations are formed and in other cases anions are formed. When cations are formed this causes a reduction in the radius, while for anions there is repulsion from added electrons therefore an increase in atomic radius is noted. However in both anions and cations, the radius decrease from left to right i.e. from Na to Al and from P to Cl. Silicon does NOT form an ion.

Unit 1 Mod 3 Period 3 elements Melting point variation Showing the melting points of period 3 elements Element M.P /C Na 98 Mg 650 Al 660 Si 1410 P 44 S 114

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Cl -101

The first 3 elements are metals. Therefore metallic bonding would be the factor involving the melting point temperature. One should appreciate that as number of valence electrons increase, this results in a stronger metallic bond. Moving from Na Al, there is an increase from 1 to 3 valence electrons, therefore stronger metallic bond i.e. increase in melting point. Silicon is a non-metal, therefore type of bonding present is covalent bonding between the silicon atoms. This results in a diamond-like structure which as one knows from experience is a very strong structure. To break covalent bonds, a lot of heat is needed i.e. a much higher melting point than any other element. From P Cl, these represent non-metals, and have P4, S8 and Cl2 molecules respectively. With discrete molecules, the factor responsible for melting point temperature is the strength of the van der Waals forces. These weak inter-molecular forces increase as the size of the atom/molecule increases, and since its a cumulative effect i.e. the more van der Waals forces, the more energy needed to break them. Therefore, the melting point drops sharply at P, increases at S and then decreases from Cl through to Ar. Electrical conductivity All metal conduct electricity because of the presence of mobile electrons. Electrical conductivity increases with increase number of valence electrons, therefore Al is a better conductor than Mg, which in turn is a better conductor than Na.

Unit 1 Mod 3 Period 3 elements

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Silicon is a semi-conductor i.e. it can conduct current only in special conditions. In all materials, conductors, semiconductors and insulators there are 2 types of bands:- valence band (where orbitals of metal atoms overlap to form a cloud of electrons) and a conduction band (higher energy level) Depending on conditions, electrons can jump from the valence to the conduction band and conduct electricity. In metals, there is no energy gap between the two bands, in insulators the energy gap is too large and thus CANNOT conduct electricity under any conditions. In semi-conductors, the energy gap is small enough to be traversed under special conditions and be able to conduct electricity. With P, S and Cl all are non-metals with no mobile electrons, therefore they are all non-conductors.

Checkpoint A

1. Sketch two graphs on the axes below to show the variation in atomic AND ionic radii for the period 3 elements

Unit 1 Mod 3 Period 3 elements

Element Na Reaction with water Sodium has a very exothermic reaction with cold water producing hydrogen and a colourless solution of sodium hydroxide. 2Na + 2H2O 2NaOH + H2 Magnesium has a very slight reaction with cold water, but burns readily in steam. Magnesium burns in steam with its typical white flame to produce white magnesium oxide and hydrogen Mg(s) + H2O(g) MgO(s) + H2(g) Aluminium powder heated in steam produces hydrogen Reaction with oxygen Burns with an orange flame to form a white solid mixture of sodium oxide and sodium peroxide 4Na + O2 2Na2O

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Reaction with chlorine Burns with an orange flame to form a white solid sodium chloride 2Na + Cl2 2NaCl

Reactions of period 3 elements with oxygen, water and chlorine

Mg

Magnesium burns in oxygen in the presence of a flame or electric spark to produce an intense white light to produce white magnesium oxide 2Mg(s) + O2(g) 2MgO(s)

Burns with an intense white flame to form magnesium chloride Mg + Cl2 MgCl2

Al

If powdered, it burns in oxygen to get white sparkles and

Burns in a stream of chlorine to form pale yellow aluminium

Unit 1 Mod 3 Period 3 elements

and aluminium oxide. The reaction is relatively slow. 2Al(s) + 3H2O(g) Al2O3(s) + 3H2(g) Si Powdered silicon burns slowly with oxygen at high temp to form silicon dioxide an hydrogen Si(s) + 2H2O(g) SiO2(s) + 2H2(g) No reaction white aluminium oxide 4Al(s) + 3O2(g) 2Al2O3(s) Slow reaction, but forms silicon dioxide if heated strongly enough Si(s) + O2(g) SiO2(s) White phosphorous catches afire spontaneously burning with a white flame to form a mixture of phosphorous (III) and (V) oxide P4 + 3O2 P4O6 P4 + 5O2 P4O10 Burns with a pale blue flame to form a colourless gas sulphur dioxide S + O2 SO2

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chloride 2Al + 3Cl2 2AlCl3

Reacts with chlorine in powdered forms to produce a colourless liquid silicon tetrachloride Si + 2Cl2 SiCl4 White phosphorous burns in chlorine to form a mixture of phosphorous(III) and (V) chloride P4 + 6Cl2 4PCl3 colourless liquid P4 + 10Cl2 4PCl5 off-white solid Reacts to form an orange awful smelling liquid 2S + Cl2 S2Cl2

No reaction

Unit 1 Mod 3 Period 3 elements

Cl Forms a combination of hydrochloric and hypochlorous acid Cl2 + H2O HCl + HOCl No reaction

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Not applicable

Reactions of period 3 oxides/chlorides with water Reaction with water Oxide Chloride

Unit 1 Mod 3 Period 3 elements

Na2O + H2O 2NaOH pH 11 very soluble MgO + H2O Mg(OH)2 pH 8 slightly soluble Al2O3 Insoluble pH 7
+

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NaCl + H2O Na (aq) + Cl-(aq) pH 7 MgCl2 + H2O Mg2+(aq) + 2Cl-(aq) slightly acidic pH 6.5 AlCl3 + 6H2O [Al(H2O)6]3+ + 3Clvery acidic pH 3 SiCl4 + 4H2O Si(OH)4 + 4HCl very acidic pH 1 PCl3 + 3H2O H3PO3 + 3HCl very acidic pH 1 PCl5 + H2O POCl3 POCl3 + 3H2O H3PO4 No reaction

SiO2 Insoluble pH 7 P4O10 + 6H2O 4H3PO4 pH 2

SO2 + H2O H2SO3 pH 1 SO3 + H2O H2SO4

Acid/base behaviour of oxides/hydroxides, including amphoteric behaviour in reaction with NaOH and acids
The oxides of sodium and magnesium are basic, thus they form alkaline solutions when dissolved in water as well as react only with acids. Reaction: O2- + H2O 2OH- e.g. \Na2O + H2O NaOH + H2O MgO is not as basic as the O2- is held very tightly by the Mg2+ ion as the cation has a greater charge than Na+ and is smaller, therefore the charge density is greater. Charge density (charge / ionic radius) influences the establishment of covalent character in ionic compounds. The HIGHER the charge density, the EASIER an anion is polarised and covalent character is shown. MgO still shows basic properties by still reacts readily with acids. Note: MgO when placed in water forms a very weakly basic solution.

Unit 1 Mod 3 Period 3 elements

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Al2O3 does not dissolve in water as the O2- ion held too tightly by the Al3+ ion. However the oxide shows its amphoteric behaviour by reacting with acids and bases. The aluminium ion is very small and highly charged, thus causes polarisation of the anion, resulting partial covalent character. The combination of ionic and covalent character results in the amphoteric behaviour of aluminium oxide. This is shown in the diagram below

Reactions of aluminium oxide showing acid and base character a) basic character Al2O3 + HCl AlCl3 + H2O b) acidic character Al2O3 + NaOH NaAl(OH)4 + H2O While the oxides of non-metals are acidic i.e. acidic solutions are formed and would only react with bases.
In general, metallic (basic) character increases down a group and decrease across (left to right) a period. Remember as the difference in electronegativities of the elements and oxygen decreases, the oxide changes from a basic to amphoteric to an acidic oxide.

Properties of period 3 oxides and chlorides Oxide Physical props Chemical Chloride props Na2O High mp Strongly Soluble in water basic oxide NaCl

Physical props High mp Soluble in water Good conductor when molten or in aq. soln

Unit 1 Mod 3 Period 3 elements

MgO High mp insoluble in water High mp insoluble in water High mp insoluble in water Basic oxide MgCl2

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High mp Soluble in water Good conductor when molten or in aq. soln Sublimes at low temp poor conductor Low mp Non-conductor

Al2O3

amphoAlCl3 teric oxide SiO2 Weakly SiCl4 acidic oxide P4O10 Low mp Acidic PCl3 Low mp Insoluble in water oxide Non-conductor SO2 Low mp Acidic SCl2 Low mp Insoluble in water oxide Non-conductor For the metallic elements excluding Al, the m.p. of the oxides/chlorides are high, and their electrical conductivity when molten is good. This indicates the presence of ions in their lattices therefore ionic bonding was present. In the case of Al, the m.p. of the oxide is not as high as expected, as the high charge density of the Al 3+ ion pulls the electron cloud from the oxide ion towards itself resulting in a high degree of covalent character. Therefore it has intermediate ionic and covalent character, and shows amphoteric behaviour. In aluminium chloride, the high charge of the metal ion causes the electrons in the anion to be pulled towards the cation forming a hybrid of ionic and covalent bonding, this results in partial covalent bonding and ultimately a lower m.p than expected. Aluminium chloride forms a DIMER (combination of two molecules) because the aluminium ion in AlCl 3 is electron deficient and needs another electron pair to complete its octet. Hence a second molecule of aluminium chloride form a weak association with each other forming a DIMER. The octet rule is a chemical rule indicating that all atoms combine in a way to ensure that they possess eight electrons in their outermost shells

Unit 1 Mod 3 Period 3 elements

Dimer of aluminium chloride

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For the non-metallic chlorides/oxides, it is shown that the m.p of both compounds, are low, they form acidic solutions and they have no electrical conductivity when melted. All of this indicates that no ions are present and the bonds between the particles are weak, the atoms within each molecule is bonded by strong covalent bonds, while the inter-molecular forces are weak Van der Waals forces.

Checkpoint B 1. Give the pH values of the solutions when the period 3 chlorides listed are placed in water [4] NaCl MgCl2 SiCl4 PCl5

2. Give the formulae of the oxides of the period 3 elements below (if there is more than one oxide, you can write either one) Na. [1] Mg.. [1] Si....[1] P.... [1]

3. Explain why Al would be more electrically conductive than Mg and why the non-metals do not conduct electricity. [3]

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Unit 1 Mod 3 Period 3 elements 4.

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