Topic 13 - Periodicity (HL)
13.1 Periodic trends Na-> Ar (the third period)
13.1.1 : (This seems very much like the last bit of SL, but now with explanations :)
Elements on the left are metallic...right are non-metals...Al is a metalloid (semi-metal).
Oxides : Non-metals -> Acidic oxides , Metals -> Basic oxides, Metalloids -> Amphoteric (both acidic & basic) oxides.
| Na2O | MgO | Al2O3 | SiO2 |
P4O10 (or P4O6) |
SO3 (or SO2) |
Cl2O7 Cl2O |
|
| Adding H2O | Na2O + H2O -> 2NaOH | MgO + H2O -> Mg(OH)2 | Insoluble | Insoluble |
P4O10 + 6H2O -> 4H3PO4 P4O6+ 6H2O -> 4H3PO3 |
SO3 + H2O -> H2SO4 SO2 + H2O -> H2SO3 |
Cl2O7 + H2O -> 2HClO4 Cl2O + H2O -> 2HOCl |
| Adding HCl | Na2O + H+ -> 2Na+ + H2O | MgO + 2H+ -> Mg2+ + H2O | Al2O3 + 6H+ -> 2Al3+ + 3H2O | No reaction | No reaction | No reaction | No reaction |
| Adding NaOH | No reaction | No reaction | Al2O3 + 2OH- + 3H2O -> 2Al(OH)4 | SiO2 + 2OH- -> SiO32- + H2O |
H3PO4 + OH- -> H2PO4- + H2O H3PO3 + OH- -> H2PO3- + H2O |
SO2 + OH- -> HSO4- SO2 + OH- -> HSO3- |
HCl2O7 + OH- -> Cl2O72- + H2O HOCl + OH- -> OCl- + H2O |
| Nature | Basic Oxide | Basic Oxide | Amphoteric Oxide | Acidic Oxide | Acidic Oxide | Acidic Oxide | Acidic Oxide |
| Conductivity | Good | Good | Good | None | None | None | None |
| Melting Point | 1275 | 2852 | 2027 | 1610 | 24 | 17 | -92 |
Explaining the physical properties ... Conductivity for ionic solutions (Na2O->Al2O3) is due to ions in solution/molten state. SiO2 is network covalent...no charges therefore no significant conductivity. Others are covalent molecules therefore no conduction. Melting point...stronger bonds when atoms can be arranged in a simple structure...MgO is highest, then Al2O3, Na2O (the ratio between the two atoms should be as close to 1 as possible). SiO2 is network covalent -> high melting point (but not as high as ionic bonding). The final 3 decrease in melting point due to decreasing polarity of molecules -> smaller dipole-dipole interactions.
Halides (assuming Cl...could replace with Br, I, F etc) : Ionic Chlorides -> dissolved in H2O with little reaction, Covalent Chlorides -> dissolve + react to form HCl.
NaCl : NaCl + H2O -> Na+ + Cl- + H2O
Good conductivity (ionic structure) MP = 801
MgCl2 : MgCl2 -> Mg2+ + 2Cl-
Good conductivity (ionic structure) MP = 714
Al2Cl6 : Al2Cl6 + 6H2O -> 2Al(OH)3 + 6HCl
Poor conductivity (Network covalent) MP = 178
SiCl4 : SiCl4 + H2O -> Si(OH)4 + 4HCl
No conductivity (Covalent molecular) MP = -70
PCl3 : PCl3 + 3H2O -> H3PO3 + 3HCl
PCl5 : 2PCl5 + 6H2O -> 2HPO3 + 10HCl
No conductivity (Covalent molecular) MP = -112
S2Cl2 Not required
Cl2 : Cl2 + H2O -> HCl + HClO (Exception : F2 is such a strong oxidizer : 2F2 + 2H2O -> 4HF + O2)
No conductivity (Covalent molecular) MP = -101
MP...NaCl and MgCl2 -> decreases due to packing (as above), drops to Al2Cl6 (network covalent). Others are covalent molecules...decreases due to decreasing polarity (Cl2 higher due to more electrons...greater LDF ?)
13.2 D-block elements (first row)
13.2.1 : Typical d-block elements are generally those exhibiting multiple oxidation states (in period 4, not Sc or Zn)
13.2.2 : The multiple oxidation states of the d-block (transition metal) elements is due to the proximity between the 4s and 3d sub shells (in terms of energy). All transition metals exhibit a 2+ oxidation state (both electrons being lost form the 4s and all have other oxidation states...ie
V - +4, +5 (apparently we need to know only 2 of these...weird if you ask me...but include Fe...
Cr - +3, +6
Mn - +4, +7
Fe - +3
13.2.3 : Ligands are the molecules which donate an electron pair to form a dative covalent bond with the central atom (thus forming a complex ion).
13.2.4 : Complex ions are molecules which carry a charge. They are formed around a central atom, with other atoms (or molecules) donating an electron pair to form a covalent bond to this central atom. Examples...
[Fe(H2O)6]3+ - Fe is the central atom, H2O is the ligand
[Fe(CN)6]3- - Fe is the central atom, CN is the ligand
[CuCl4]3- - Cu is the central atom, Cl is the ligand
[Cu(NH3)4]2+ - Cu is the central atom, NH3 is the ligand
[Ag(NH3)2]+ - Ag is central atom, NH3 is the ligand
13.2.5 : The color in the transition metals (d-block) is predominantly due to the splitting of the d shell orbitals into slightly different energy levels. As a result, certain wavelengths of energy can be absorbed by the d-block elements (with electrons jumping between these slightly different energy levels), resulting in the complement color being visible.
13.2.6 : d-block elements make good catalysts due to their multiple oxidation states (hence their ability to react with different species and produce a path of lower activation energy, and so allow the reaction to proceed at a faster rate). Examples...
MnO2 in decomposition of hydrogen peroxide
V2O5in the contact process
Fe in Harber process
Ni in conversion of alkenes to alkanes