Group I, II and the Halogens

Group 1: Alkali Metals Lithium – Li, Sodium – Na, Potassium – K, Rubidium – Rb, Caesium – Cs. Group 2: Beryllium – Be, Magnesium – Mg, Calcium – Ca, Strontium – Sr, Barium – Ba. Metallic Bonding: The electrostatic attraction between the cations and the delocalised sea of electrons Melting Point decreases down group because:   Down group, the size of the ion increases. Therefore the metallic bonding is weaker as the sea of electrons is further away from the positive protons

Flame test: Dip nichrome wire into HCl and then heat in Bunsen burner. Repeat until no colour produced Metal ion Li+ Na+ K+ Rb+ Cs+ Be2+ Mg2+ Ca2+ Sr2+ Ba2+ Colour Red Orange Lilac Red Blue Infra-red Infra-red Brick Red Red Green

When the electrons are given heat energy by the Bunsen, they jump to a higher energy level. When the electrons move back down to their energy levels, they emit energy as light, and their colour depends on the frequency of the light emitted.

Reaction w/ water: Group 1 generally happens faster than Group 2. Reactivity decreases down group 2K(s) + 2H2O(l) → 2KOH(aq) + H2(g) Or Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g) Observations:  Fizzing  Gets smaller and the disappears  Melts into ball (not Li) Be does not react with steam or water Mg reacts very slowly with water but faster with steam Group 2 Reaction w/ Oxygen: 2Ca(s) + O2(g) → 2CaO(s) Reaction w/ Chlorine: Ca(s) +Cl2(g) → CaCl2(s)  All ions except for BeCl2, which is covalent (Be2+ is a small ion and has a high charge. Therefore very Polarising, which leads to the distortion of the Cls and covalency). Reaction of Oxides w/ water: When they react with water an alkaline solution is formed. O2- + H2O → 2OHReaction of Oxides w/ an acid: O2- + 2H+→ H2O Solubility of Group 2 Salts: Hydroxides:  Solubility increases down group

Be(OH)2 Mg(OH)2 Ca(OH)2 Sr(OH)2 Ba(OH)2
Insoluble Quite soluble

Sulphates:  Solubility decreases down group

Be(OH)2 Mg(OH)2 Ca(OH)2 Sr(OH)2 Ba(OH)2
Very soluble Insoluble

Only soluble if it is a big molecule with a small molecule Stability of Carbonates Group 1 carbonates are all thermally stable in the Bunsen, except for Li2CO3 which acts as if it were group 2 (because it is such a small ion) Group 2 carbonates (and Li2CO3) decompose to their Oxides in the Bunsen. E.g. CaCO3(s) →CaO(s) + CO2(g) The higher the charge & the smaller the cation, the more polarising it is & the more it distorts the CO32-, weakening its bonds, which means that it is less stable. Therefore the stability of the carbonate increases down group as the cation is larger. Test: Bubble gas produced through limewater, if the carbonate decomposes, the lime water will turn cloudy. Nitrates: NO3- is a large polarisable ion.   Stability of nitrates increases down group. As the size of cation decreases, the more the nitrate ion is distorted, and the weaker the bonds, so the nitrate is less stable. Group 1 nitrates (except LiNO3) are more stable than group 2, as they have less charge and are bigger than their adjacent group two cation.

Group 2 decomposes to form the oxide, nitrogen dioxide (brown gas) and oxygen: 2Ca (NO3)2 → 2CaO + 4NO2 + O2 (Measure the time taken for the brown gas to appear or for a glowing splint to relight) Group 1 decomposes into nitrite and oxygen (except LiNO3 because other group 1 cations are not polarising enough to break down the nitrite into NO 2) 2NaNO3 → 2NaNO2 + O2

Halogens Halogen Fluorine – F2 Chlorine – Cl2 Bromine - Br2 Appearance Pale yellow gas Green gas Brown liquid, Orange in solution Dark Grey solid Purple gas Brown in solution Purple in organic solvent

Iodine - I2

Extracting Iodine into organic solvent:   Tests: Cl – bleaches damp litmus paper Br – bleaches damp litmus paper slowly I – turns starch blue/black Oxidising power if the Halogens: X2 +2e- → 2XOxidising agent as it is reduced, and it oxidises something else The stronger X2 is an oxidising agent, the more favourable the process is. The oxidising power of X2 (ability to attract e-) depends on: a) Atomic radius increases, the attraction of extra e- decreases b) No. of e- shells increase, the shielding increases, and therefore the attraction decreases c) These affects outweigh the increasing nuclear charge. NaCl NaCl NaBr NaI Yellow/orange colour Brown colour and/or black precipitate NaBr ----NaI --------Brown colour and/or black precipitate Put aqueous Iodine + organic solvent in a test-tube (two layers should form) Shake briskly, and the layers will mix and the solution will turn purple

Oxidising power: F2>Cl2>Br2>I2

Displacement order: F2>Cl2>Br2>I2 Bromine is extracted from sea water. It is done by oxidising Br- with Cl2 Iodine is a strong reducing agent (good at losing electrons): a) Atomic radius increases, the ability to lose an electron as the distance fromm the positive protons is larger b) No. of e- shells increase, the shielding increases, and therefore the attraction decreases, meaning the ability to lose electrons increases Reducing Power: I2>Br2>Cl2>F2 Reaction of solid sodium halides with concentrated H2SO4: 2X- → X2 + 2eH2SO4 (oxidation no. +6) can be reduced to: SO2 (ox. no. +4), S (ox. no. 0) and H2S (ox. no. -2) NaX NaCl NaBr Observations Steamy fumes Steamy fumes Brown gas (colourless gas) Steamy fumes (colourless gas) Yellow solid Purple fumes Bad smell of eggs Products HCl HBr Br2 SO2 HI SO2 S I2 H2S Types of reaction Displacement Displacement Br- ox. product H2SO4 red. product Displacement H2SO4 red. Product H2SO4 red. Product H2SO4 red. Product I- ox. product

NaI

Equations: Chloride: NaCl + H2SO4 → NaHSO4 + HCl Bromide: NaBr + H2SO4 → NaHSO4 + HCl   H2SO4 + 2H+ + 2e- →SO2 + 2H2O 2Br- → Br2 + 2e-

H2SO4 + 2Br- + 2H+ →SO2 + Br2 + 2H2O

Iodide:

NaI + H2SO4 → NaHSO4 + HI   H2SO4 + 2H+ + 2e- →SO2 + 2H2O 2I- → I2 + 2e-

H2SO4 + 2I- + 2H+ →SO2 + I2 + 2H2O  H2SO4 + 6H+ + 6e- →S + 4H2O  2I- → I2 + 2eH2SO4 + 6I- + 6H+ →S + 3I2 + 4H2O  H2SO4+ 8H+ + 8e- →H2S + 4H2O  2I- → I2 + 2eH2SO4 + 8I- + 8H+ →H2S + 4I2 + 4H2O Hydrogen Halides: HX → H+ + XHX very soluble & dissolves forming an acidic solution HX +H2O → H3O+ + XHCl, HBr, HI all are strong acids H-F weaker because the bond is so strong that H+ is not formed Acidity increases down group. Tests: ClBrIHNO3 + AgNO3 White ppt. Cream ppt. Yellow ppt. Then with dilute NH3 Dissolves Insoluble Insoluble Then with conc. NH3 Dissolves Dissolves Insoluble

N.b. The HNO3 is to remove any impurities which would react with the AgNO3 Reaction of Cl with NaOH: At 15⁰C: o 2NaOH + Cl2 (ox. no. Cl: 0) → NaClO (ox. no. Cl: 1) + NaCl (ox. no. Cl: -1) + H2O o Disproportionation reaction because Cl is oxidised and reduced simultaneously At 80⁰C: o 3OCl- (ox. no. Cl: +1)→ 2Cl- (ox. no. Cl: -1) + ClO3- (ox. no. Cl: +5) o Dispropotionation reaction

Test

Cl-

Br-

I-

H2O2 + H2SO4 Then add starch H2O2 + H2SO4 is an oxidising agent

Turns Brown (I2(aq)) Turns Blue/black