CHAPTER 10 CHEMICAL PERIODICITY
Learning Outcomes
describe qualitatively (and indicate the periodicity in) the variations in atomic radius, ionic radius, melting point and electrical conductivity of the elements explain qualitatively the variation in atomic radius and ionic radius interpret the variation in melting point and in electrical conductivity in terms of the presence of simple molecular, giant molecular or metallic bonding in the elements explain the variation in first ionisation energy describe the reactions, if any, of the elements with oxygen (to give Na2O, MgO, Al 2O3, P4O10, SO2, SO3), chlorine (to give NaCl , MgCl 2, Al 2Cl 6, SiCl 4, PCl 5) and water (Na and Mg only) state and explain the variation in oxidation number of the oxides and chlorides in terms of their valance shell electrons
Learning Outcomes
describe the reactions of the oxides with water [treatment of peroxides and superoxides is not required] describe and explain the acid/base behaviour of oxides and hydroxides including, where relevant, amphoteric behaviour in reaction with sodium hydroxide (only) and acids
describe and explain the reactions of the chlorides with water
suggest the types of chemical bonding present in chlorides and oxides from observations of their chemical and physical properties predict the characteristic properties of an element in a given group
by using knowledge of chemical periodicity
deduce the nature, possible position in the Periodic Table, and identity of unknown elements from given information about
physical and chemical properties
Periodic Table
Old periodic table (1869) By Russian Mendeleev and German Meyer Elements arranged in order of atomic mass Elements with similar chemical properties
fell in the same column.
The Periodic Law And The Periodic Table
Periodic law
law stating that many of the physical and chemical
properties of the elements tend to occur in a systematic manner with increasing atomic number.
Periodic table
is a tabular arrangement of the elements in order of
increasing atomic number such that elements
having similar chemical properties are positioned in vertical column
Period 3 Elements (Na Ar)
Period 3
Trends In Atomic Size
Radius
Atomic Radius = half the distance between two nuclei of a diatomic molecule.
Trends in Atomic Size
Influenced by three factors: 1. Energy Level
2. Charge on nucleus 3. Shielding effect
Periodic Trends
As you go across a period, the radius gets smaller. This is caused by the increase in nuclear charge and weak screening effect as successive electrons are added to the same quantum shell.
Na
Mg
Al
Si
P S Cl Ar
Overall
Trends in Ionization Energy
There is a general increase in first I.E. as atomic number increases because: a) The nuclear charge increases, due to increase in number of protons and electrons. b) The radius of atom decreases with increasing atomic number, hence more energy required to remove outer electrons.
Trends in Ionization Energy
So IE generally increases from left to right. Exceptions at full and 1/2 full orbitals.
Trends in Ionic Size
Cations are smaller than their respective atoms. Anions are bigger than their respective atoms.
Size of Isoelectronic ions
Iso- means the same Iso electronic ions have the same number of electrons Al3+ Mg2+ Na1+ Ne F1- O2- and N3all have 10 electrons 2 2 6 all have the configuration: 1s 2s 2p
Size of Isoelectronic ions
Al3+
In an isoelectronic series (Na to Si) and (P to Cl), ionic radius decreases as the proton number increases. This is because the same number of electrons are attracted more strongly by the increasing nuclear charge. 3N Positive ions that have more protons would be 2F1- O smaller. 1+ Ne
Na
Mg2+
Changes in melting points
To understand these changes we must understand the nature of the bonding within the elements. Three types of structure occur as we cross period 3. 1) Metallic Structures, Na, Mg, Al 2) Giant Molecular, Si 3) Molecular Structures, P4, S8, Cl2 and Ar P4 < S8 > Cl2 > Ar
Variation in Electrical Conductivity
Electrical conductivity is relatively high for metals, lower for the metalloids and almost negligible for non-metals.
Chemical properties
Oxides Most metallic elements, both metals and nonmetals, combine directly with oxygen. Metallic elements form ionic oxides whilst non-metallic elements form covalently bonded oxides. For example: 2Mg(s) + O2(g) 2MgO(s)
Chemical properties
Chlorides There are a number of methods for preparing chlorides. The direct preparation can be used although the reaction can be vigorous. For example: 2Al(s) + 3Cl2(g) 2AlCl3(s)
Chemical properties
The table below summarises the most common oxides and chlorides of Period 3 elements.
Element Na Mg Al Si P S Oxide Na2O MgO Al2O3 SiO2 P2O5 SO2 Chloride NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl2
Cl
Cl2O
Cl2
Oxidation Number
Oxides (Na to S)
The oxygen in the compound is always the more electronegative element (oxidation number -2). The maximum oxidation number is the same as the group number. P and S show several oxidation numbers (depends on the number of electrons used for bonding).
Na in Na2O +1 Mg in MgO +2 Al in Al2O3 Si in SiO2 P in P4O10 +3 +4 +5
S in SO3
S in SO2
+6
+4
Oxidation Number
Chlorides Chlorine in the compound is the more electronegative element (has a negative oxidation number -1)
Na
Mg Al Si P
+1
+2 +3 +4 +5
In each case the oxidation number is the same as the number of electrons in the outer energy level of the atom
Reaction of oxides with water
The physical properties of these oxides depend on the type of bonding.
Element
Na
Formulae of oxide
Na2O
Structure of oxide
Ionic
Melting point of oxide /C
1275
Mg
Al Si P S
MgO
Al2O3 SiO2 P4O10 SO3
Ionic
Mostly Ionic Giant Covalent Simple Covalent Simple Covalent
2852
2072 1703 300 -10
Na2O, Al2O3 and MgO - high melting point. MgO and Al2O3 have a higher melting point than Na2O since the charges are higher and the atomic radii smaller, resulting in a stronger electrostatic attraction (forces) between the ions. P4O10 and SO3 have a much lower melting points.
Acid-base properties of the oxides of Period 3
Element Formulae of oxide Acid-base character of oxide pH of solution when dissolved in water Na Na2O Basic Mg MgO Basic Al Al2O3 Amphoteric Si SiO2 Acidic P P4O10 Acidic S SO2 SO3 Acidic
12 - 14
8-9
7 (insoluble)
7 (insoluble)
2-4
2-4
13
The oxides therefore become more acidic on moving from left to right in the periodic table
Reaction of Chlorides with water
NaCl and MgCl2 are ionic chlorides - melting point is high. AlCl3 and SiCl4 are molecular covalent chloride - melting points are thus much lower than the ionic chlorides. AlCl3 actually exists in polymeric form in the solid state, which is converted to a dimeric form in the gas phase. At high temperatures, it reverts to a simple molecular structure. PCl5 is ionic so its melting point is thus high. On heating, however, it reverts to a simple covalent structure and sublimes.
Reaction of Chlorides with water
The way in which chlorides react with water depends on the type of bonding present in the chloride: Ionic chlorides dissolve in water to give neutral solutions:
NaCl(s) Na+(aq) + Cl(aq)
pH = 7 pH = 7
MgCl2(s) Mg2+(aq) + 2Cl(aq)
Aluminium chloride reacts with water to give hydrated aluminium ions and chloride ions. The hydrated aluminium ions undergo deprotonation to give an acidic solution:
AlCl3(s) + 6H2O(l) [Al(H2O)6 ] (aq) + 3Cl(aq) Al(H2O6) (aq) + H2O(l) [Al(H2O)5(OH)]2+(aq) + H3O+(aq)
Reaction of Chlorides with water
The other covalent chlorides react readily with water at room temperature to form the oxide or hydroxide and HCl(g). The HCl is formed as white misty fumes, and the observance of these fumes is a good indication that the chloride is covalent. SiCl4(l) + 2H2O(l) SiO2(s) + 4HCl(g) pH = 1 - 2 PCl5(s) + 4H2O(l) H3PO4(aq) + 5HCl(g) pH = 1 - 2
