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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.

. Hence the electrons in a covalent bond are attracted less to the halogens.---à X-(g) The electron affinity increases from fluorine to chlorine and then decreases from chlorine to iodine. 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.ii) Electronegativity Page 2 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. X(g) + e.

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

à 2 NaBr(s) moderate 2 Na(s) + I2 --.Page 3 iv) Bond enthalpy The bond enthalpy is the energy required to break 1 mole of covalent bonds in gaseous state. It is because the increase in atomic size down the group leads to the increase in bond length.54V 3+ 2+ Fe (aq) + e ---à Fe (aq) E = +0.---à 2 Cl-(aq) E = +1.---à 2 Br-(aq) E = +1. the unusually short F-F bond length leads to very high repulsion between the non-bonded electrons of each fluorine atom.à 2 NaI(s) moderate ii) Reaction with iron(II) ion Cl2(aq) + 2 e.07V I2(aq) + 2 e.à 2 I-(aq) E = +0.à 2 NaCl(s) violent 2 Na(s) + Br2 --. X2(g) ---à 2 X(g) The bond enthalpy of fluorine is lower than expected.77V . Hence F-F bond is weaker than expected.à 2 NaF(s) explosive 2 Na(s) + Cl --. Relative oxidizing power of halogens Relative oxidizing power: F2 > Cl2 > Br2 > I2 i) Reaction with sodium 2 Na(s) + F2 --. The bond enthalpy for other halogens decreases in the order of: Cl2 > Br2 > I2 .--. Since the size of fluorine atom is very small.36V Br2(aq) + 2 e. Hence the strength decreases.

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à 5 NaI(aq) + NaIO3(aq) + 3 H2O(l) . concentrated 3 Cl2(aq) 6 NaOH(aq) ---à 5 NaCl(aq) + NaClO 3(aq) + 3 H2O(l) For Br2 . dilute hot. 3 Br2(aq) 6 NaOH(aq) ---à 5 NaBr(aq) + NaBrO3(aq) + 3 H2O(l) For I2 . 3 I2(aq) 6 NaOH(aq) --. atom or ion) is simultaneously oxidized and reduce. dilute hot. 2 F2(g) + 2 NaOH(aq) ---à 2 NaF(aq) + OF2(g) + H2O(l) 2 F2(g) + 4 NaOH(aq) ---à 4 NaF(aq) + O2(g) + 2 H2O(l) For Cl2 . Cl2(aq) + H2O(l) ---à HCl(aq) + HOCl(aq) For F2 .Page 4 iii) Reaction with phosphorus 2 P(s) + 5 F2(g) ---à 2 PF5(s) 2 P(s) + 5 Cl2(g) ---à 2 PCl5(s) 2 P(s) + 3 Cl2(g) ---à 2 PCl3(s) 2 P(s) + 3 Br2(g) ---à 2 PBr3(s) 2 P(s) + 3 I2(g) ---à 2 PI3(s) Disproportionation of the halogens in alkalis Disproportionation is a chemical change in which one particular species (molecule. concentrated cold. Cl2(aq) + 2 NaOH(aq) ---à NaCl(aq) + NaOCl(aq) + H2O(l) cold.

Page 5 Comparative study of the reactions of halide ions i) with halogens The stronger oxidizing halogen can displace (oxidize) other halide ions.g. 3 NaCl(s) + H3PO4(l) ---à Na3PO4(s) + 3 HCl(g) 3 NaBr(s) + H3PO4(l) ---à Na3PO4(s) + 3 HBr(g) 3 NaI(s) + H3PO4(l) ---à Na3PO4(s) + 3 HI(g) . the hydrogen halides will not be oxidized to halogens. However HBr is fairly easily oxidized to bromine and HI can be easily oxidized to iodine. F2(aq) + 2 Cl-(aq) ---à 2 F-(aq) + Cl2(aq) Cl2(aq) + 2 Br-(aq) ---à 2 Cl-(aq) + Br2(aq) Cl2(aq) + 2 I-(aq) ---à 2 Cl-(aq) + I2(aq) Br2(aq) + 2 I-(aq) ---à 2 Br-(aq) + I2(aq) ii) with concentrated sulphuric(VI) acid For F.and Cl.ions. NaF(s) + H2SO4(l) ---à NaHSO4(s) + HF(g) NaCl(s) + H2SO4(l) ---à NaHSO4(s) + HCl(g) For Br-ion. NaBr(s) + H2SO4(l) ---à NaHSO4(s) + HBr(g) 2 HBr(g) + H2SO4(l) ---à Br2(g) + SO2(g) + 2 H2O(l) overall: 2 NaBr(s) + 3 H2SO4(l) ---à 2 NaHSO4(s) + SO2(g) + Br2(g) + 2 H2O(l) For I-ion. 3 NaX(s) + H3PO4(l) ---à Na3PO4(s) + 3 HX(g) e. NaI(s) + H2SO4(l) ---à NaHSO4(s) + HI(g) 8 HI(g) + H2SO4(l) ---à 4 I2(g) + H2S(g) + 4 H2O(l) overall: 8 NaI(s) + 9 H2SO4(l) ---à 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 . 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).