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The p-Block Elements

The halogens Halogens contain fluorine, chlorine, bromine, iodine (and highly unstable astatine). Characteristic properties of the halogens All halogens have i) high electronegativities. ii) high electron affinities. These show that halogens have a high tendency to attract electrons. Usually halogens have the oxidation state of 1 in their ionic or covalent compounds. e.g. HF , HCl, NaCl Fluorine being the most electronegative element should have the oxidation state of 1 in its compound. However, Cl , Br anf I may have the oxidation state other 1. e.g. Cl2O , ClO3 , BrO-, IO3- ,..

Variation in properties of the halogens and their compounds i) Melting point and boiling The melting /boiling point increases down the group because the molecular mass increases down the group and hence the intermolecular (van der Waals) force increases.

ii) Electronegativity

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The electronegativity decreases down the group because the outer electrons become progressively Better shielded from the nucleus as the atomic size and number of inner electron shells increase. Hence the electrons in a covalent bond are attracted less to the halogens. iii) Electron affinity

The electron affinity is the enthalpy cha nge when 1 mole of a gaseous atoms acquire an electron to give gaseous ions. X(g) + e- --- X-(g) The electron affinity increases from fluorine to chlorine and then decreases from chlorine to iodine.

Reasons: a) the increase in atomic size and number of electron shells down the group lead to the decrease in effective nuclear charge. b) The atomic size is very small, the addition of an electron produces an important electron-electron repulsion. Hence its electron affinity is lower than expected.

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iv) Bond enthalpy

The bond enthalpy is the energy required to break 1 mole of covalent bonds in gaseous state. X2(g) --- 2 X(g)

The bond enthalpy of fluorine is lower than expected. Since the size of fluorine atom is very small, the unusually short F-F bond length leads to very high repulsion between the non-bonded electrons of each fluorine atom. Hence F-F bond is weaker than expected. The bond enthalpy for other halogens decreases in the order of: Cl2 > Br2 > I2 . It is because the increase in atomic size down the group leads to the increase in bond length. Hence the strength decreases.

Relative oxidizing power of halogens Relative oxidizing power: F2 > Cl2 > Br2 > I2 i) Reaction with sodium 2 Na(s) + F2 --- 2 NaF(s) explosive 2 Na(s) + Cl --- 2 NaCl(s) violent 2 Na(s) + Br2 --- 2 NaBr(s) moderate 2 Na(s) + I2 --- 2 NaI(s) moderate

ii) Reaction with iron(II) ion

Cl2(aq) + 2 e- --- 2 Cl-(aq)

E = +1.36V

Br2(aq) + 2 e- --- 2 Br-(aq) E = +1.07V I2(aq) + 2 e- --- 2 I-(aq) E = +0.54V 3+ 2+ Fe (aq) + e --- Fe (aq) E = +0.77V

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iii) Reaction with phosphorus 2 P(s) + 5 F2(g) --- 2 PF5(s) 2 P(s) + 5 Cl2(g) --- 2 PCl5(s)
2 P(s) + 3 Cl2(g) --- 2 PCl3(s)

2 P(s) + 3 Br2(g) --- 2 PBr3(s) 2 P(s) + 3 I2(g) --- 2 PI3(s)

Disproportionation of the halogens in alkalis Disproportionation is a chemical change in which one particular species (molecule, atom or ion) is simultaneously oxidized and reduce.

Cl2(aq) + H2O(l) --- HCl(aq) + HOCl(aq) For F2 , 2 F2(g) + 2 NaOH(aq) --- 2 NaF(aq) + OF2(g) + H2O(l) 2 F2(g) + 4 NaOH(aq) --- 4 NaF(aq) + O2(g) + 2 H2O(l) For Cl2 , Cl2(aq) + 2 NaOH(aq) --- NaCl(aq) + NaOCl(aq) + H2O(l)

cold, dilute hot, concentrated

cold, dilute hot, concentrated

3 Cl2(aq) 6 NaOH(aq) --- 5 NaCl(aq) + NaClO 3(aq) + 3 H2O(l) For Br2 , 3 Br2(aq) 6 NaOH(aq) --- 5 NaBr(aq) + NaBrO3(aq) + 3 H2O(l) For I2 , 3 I2(aq) 6 NaOH(aq) --- 5 NaI(aq) + NaIO3(aq) + 3 H2O(l)

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Comparative study of the reactions of halide ions i) with halogens The stronger oxidizing halogen can displace (oxidize) other halide ions. F2(aq) + 2 Cl-(aq) --- 2 F-(aq) + Cl2(aq) Cl2(aq) + 2 Br-(aq) --- 2 Cl-(aq) + Br2(aq) Cl2(aq) + 2 I-(aq) --- 2 Cl-(aq) + I2(aq) Br2(aq) + 2 I-(aq) --- 2 Br-(aq) + I2(aq) ii) with concentrated sulphuric(VI) acid For F- and Cl- ions, NaF(s) + H2SO4(l) --- NaHSO4(s) + HF(g) NaCl(s) + H2SO4(l) --- NaHSO4(s) + HCl(g) For Br-ion, NaBr(s) + H2SO4(l) --- NaHSO4(s) + HBr(g) 2 HBr(g) + H2SO4(l) --- Br2(g) + SO2(g) + 2 H2O(l) overall: 2 NaBr(s) + 3 H2SO4(l) --- 2 NaHSO4(s) + SO2(g) + Br2(g) + 2 H2O(l) For I-ion, NaI(s) + H2SO4(l) --- NaHSO4(s) + HI(g) 8 HI(g) + H2SO4(l) --- 4 I2(g) + H2S(g) + 4 H2O(l) overall: 8 NaI(s) + 9 H2SO4(l) --- 8 NaHSO4(s) + 4 I2(g) + H2S(g) + 4 H2O(l)

The difference between reactions of halide ions with concentrated H2SO4 is due to HF and HCl cannot be oxidized by concentrated H2SO4 . However HBr is fairly easily oxidized to bromine and HI can be easily oxidized to iodine.

iii) with phosphoric(V) acid Halide ions react with phosphoric(V) acid to form the hydrogen halides. Since phosphoric(V) acid is not a oxidizing agent (concentrated H2SO4 is a strong oxidizing agent), the hydrogen halides will not be oxidized to halogens. 3 NaX(s) + H3PO4(l) --- Na3PO4(s) + 3 HX(g) e.g. 3 NaCl(s) + H3PO4(l) --- Na3PO4(s) + 3 HCl(g) 3 NaBr(s) + H3PO4(l) --- Na3PO4(s) + 3 HBr(g) 3 NaI(s) + H3PO4(l) --- Na3PO4(s) + 3 HI(g)