chapter 16) THE HALOGENS (GROUP VIIA) 537 Para per-iodic acid, H,1O, has central iodine atom surrounded by five OH groups and one oxygen atom in an octahedral manner (Figure 16.6). oO HO. OH Ww. HO—I=0O HO (2) OH (>) Fig. 16.6, Structure of HIO, (a) Attachment of OH group and O around I. (6) Arrangement of groups and atoms in octahedral manner. INTERHALOGEN COMPOUNDS STRUCTURAL “AND CHEMICAL ASPECTS : ° The binary compounds of halogens among themselves: are called interhalogen compounds. Four types of such compounds are known, namely XX’, XX,', XX,’ and XX,'. They are regarded halides of the more electrdpositive components. Thus, CIF is called chlorine monofluoride and ICI, iodine frichloride. The halogen atoms in interhalogen compounds are linked by covalent bonds in exactly the same manner as halogen atoms among themselves to form molecules. As a result of the electronegativity between X and X’ halogen atoms the interhalogen compounds show polarity in bonds. Thus ICI, ICI, and BrF, show certain ionic character in their bonds. . The interhalogens consists of a larger halogen atom (X) surrounded by smaller halogen atoms (X'). Geometrical limitations restrict the formation of certain possible interhalogens. For example,-BrF, does not exist whereas IF, has Let us now discuss the interhalogen compounds under the four gereral types, ie., XX’, XX", XX, and XX,', XX! TYPE INTERHALOGENS Only five interhalogens of this type are known Chlorine monofluoride CIF (Colourless 25, bp — qwl'C) Bromine monofluoride —BrF (Pale brown gas. bp =¥°O) Bromine monochloride BrCl gasINORGANIC CHEMISTp, 538 * 1cl (a form F lodine monochloride B form - brownish-red solid, mp, 14°C) (Grey solid, m.p. 42°C) a colourless gas which liquefies to a Yello h characteristic odour. f Cl, and F, at room temperature, lodine monobromide IBr Chlorine monofluoride, CIF is liquid and solidifies to colourless solid wit Nis prepared by the direct combination 0} Cl,+F, ——> 2ClF CIF undergoes reactions similar to that of F,. Structure Chlorire monofluoride has linear structure v :Cl —F : BROMINE MONOFLUORIDE, BrF It condenses to dark red liquid which freezes to a yellow crystalline solid. \% Gaseous bromine reacts with F, at $0°C to give BrF. Br,+F, ——+ 2BrF -ErF is reactive and decomposes to BrF3 and BrFs along with free bromine. ‘ . . ' 3BrF ——> BrF, + Br, : SBF ——+ BrF, + 2Br, , _ Todine moncfuoride does not exist. IODINE MONOCHLORIDE, ICI It exists as red transparent crystals which melt to brownish-red liquid. The liquid boils at é . buts ion ae 100°C to red vapour with a choking smell. The vapours cause bad Preparation Ai) Mis prepared an . . 35°C ioro4 ha cading iodine to liqu*4 chlorine and keeping the mixture at L+Ch —+ 2Ici (i) An aqueous i solut Saas acae 7 . 4 liberate C] 'on of potassium iodide and iodate react with HCI to ae *SKI+6HCL —, 31, +3H,0 +4 6KCI ,* 21,4 6HCL —_, x14 sici+ 3H,0HE HALOGENS (GROUP VA) sie ou jenagtee 6% properties chloride is hydrolysed in aqueous solutions to liberate j _ s}cl+3H,0 ——> WO, +21, +5HCI al Liquid iodine monochloride is a good solvent and dissociates as: 2Icl ——> TI'+ [Ici yy alkali metal chlorides dissolve in ICI except LiCl, NaCl to give KCI +3Cl ——> "(ICI PCI, SbCl, SnCl, AICI, etc., react with ICI to ionising acidic solution. ICl+PCl, ——> lfrciJ- HCI reacts with ICI to form a strong acid, HICI,. HCI+1Cl ——+ H[ICIJ" cl Y : : cl Structure : Iodine monobromide, JBr is also obtained by the direct combination of I, and Br,. . : . . . 1,+Br, ——> 2Br XX’; Type Interhalogens : Only three interhalogen compounds of XX‘, type are known: Chlorine trifluoride CIF, (Colourless gas, bp. 12°C) BrF, (Greenish -yellow liquid, bp. 127.6°C) ICI, (Orange~ -yellow solid, melts with decomposition at 101°C) Bromine trifluoride Iodine trichloride Chloride trifluoride, CIF; The colourless gas is obtained by direct combini excess F, at 250°C in a nickel tube. Cl) + 3F; ——— 2CiFs ation of Cl, or CIF andee 540 7 Tr reacts with glass and attacks many compounds and most of the clemens, It reacts with water giving 4 loud crac! Structure Microwave data have shown planar structure for CIF, cl “> fo 87° \ ‘ F 1L6A F F Bromine trifluoride, BrF, . : It is prepared by mixing bromine vapours with excess F, in presence of nitrogen. . Nz Br,+3F, ——> 2BrF3 BrF, is a good ionizing solvent. 2BrF, ——+ [BrF,*] + (BrF,] It reacts with metals and metal oxides to compounds of the type: [BrF,*) [AUF], [BrF,]* [SbF] Structure . The structure of BrF, is T-shaped. . 1.78 A° Br———F 86° 1.78 A° F Iodine trichloride, ICI; It can be obtained pure as lemon yellow crystals. Preparation (i) IC), can be prepared by direct combination of e'lements, For this pup chlorine is passed on iodine at - 80°C or Cl, is passed over iodine until | is formed and then raising the temperatures to 100°C, 1,+3Cl, — aici, (ii) ICI, can also be obtained by heating 1,0, in prese:nce of HCI. 1,0, + 1OHC] —_+ 2ICl, + 2C1, + 5H,O} THE HALOGENS (GROUP ViIA) 16] yonsetes properties " S44 1Cl, is easily hydrolysed by water. / 21CI, + 34,0 ——> IC1+HIO, + sHcI IC, reacts with CS, to give CCl,. > 3CS, + 41Cl, ——> CCl,+2CSCI, + 2S.Cl, + 21 Icl, combines with metal chlorides to form compounds ofthe type MICL. YPE MUG, Structure X-ray analysis of the crystal of ICI, has given it a dimeric structure. , | cl al LIAS, 9 wv > yee. ork: Aa / NS cl cl cl XXy' Type Interhalogens . * Only two interhalogens of this type are known: . Bromine pentafluoride BrF, (Colourless liquid, b.p. 40.5°C) Iodine pentafluoride IF, (Colourless liquid, b p. 98°C) * Both are fairly thermally stable. urumine Pentafluoride, BrFs Ii is prepared by passing F, through BrF, product to 290°C. , It is fairly stable but reacts chlorides. It reacts violently with water. Structure : The structure © at 100°C and heating the gaseous readily with alkali metals, non-metals and their { BrF, is square pyramidal. FINORGANIC CHEMISTRy, 542 Todine pentafluoride, IFs Preparation . . 6) mt can be prepared by the action of I, on AgF. ‘ M,+AgE ——> JF, + 5Agl (i) _F, reacts with hot 1,0, to give IF,. 21,0, + 10F, ——> 4IF, +50, (iii) By the direct action of F, overheated iodine in a squartz vessel. Propertics a (i) _ IF, is quite reactive and fumes in air. It is readily hydrolysed by water, 2IF, + 5H,O ——> 1,0,+ 10HF Gi) IF, reacts with most of the elements. Thus it combines with mercury to form Ha(IF,);. . S, P, Si, Bi, etc., react violently with iw=ndescence. IF, reacts with 1,0,, P,O,, V,0,, C -, etc., to form dxyfluorides, ie., 10F, POF,, VOF, and CrO,F,, respectively. MoO, and WO, react with IF, to give addition products, 2Mo,. 3IF, end WO,. 2IF,. . (iv) ICI reacts with CCI, to form a mixture of CCI,F, ICI and ICI, CCl, +IF, ——+ CCIF+ICI+ICl, (v) Certain Potassium salts react with IF, to give addition products. KIO,+ IF, ——+ KIO,.IF, KF+IF, ——+ KIF, Gi) Structure Infrared, Raman and Nuclear Magnetic Resonance spectroscopy have shown molécule to have tetragonal pyramid structure: F[Chapter 16] THE HALOGENS (GROUP via ) XX,' Type Interhalogens = ‘The only interhalogen known for XX," type is IF, x, is IF, Iodine heptafluori ii Ptafluoride, IF, is prepared by the passing F, through liquid iodine pentafluoride at 90°C eas and then Passing the mixture through 2 platinum tube IFy+F, —— 1, - (IF, molecule is ii i without ; le is inert because iodine possesses its maximum covalency in it any lone pair pf electrons. However, it is hydrolysed by water. IF, +6H,0 ——>+ 7HF +H,I0, Jn acts as a fluorinating gent in presence of HgF, at 350°C Thus, it fluorinates CCI,F, to CCIF,. . . CCLF,+IF, ——> CCIE, Structure IF, molecule involves dsp’ hybridization and has pentagonal bipyramidal structure. PSEUDOHALOGENS dicals show behaviou e called r analogous to halogens and are call ers just Certain ra pee Prades earn sof peudohloges a2 Cyanogen (CN), + Thiocyanogen (SCN); Selenocyanogen (SeCN), Azidocarbondisulphide (SCSN,),INORGANIC CHEMISTRY 544 They are usually prepared by methods similar to those used for the preparation bic uni ue Agt(CD, He(CN), + HgCl; —— He,Cl + (CN): v7 2AgSCN + Br; —— 2AgBr + (SCN); L/ QAwSeCN +1; > 2Agl + (SeCN); MnO. =2HCN ——> Mn(CN); + (CN); + 2H,O “MnO, + 4HCl ——> MnCl, + Cl, + 2H; Azidocarbondisulphide (SCSN,), is prepared es white crystals from CS, and + potassium azide. 40°C H:03 CS,+KN, ——> KSCSN, ° (SCSN,); (SCSN;), decomposes at room temperature to give N., S and (SCN),. (SCSN,), ——> 2S+2N;+ (SCN); Points of Similarities Between Pseudohalogens and Halogens The following points of similarity are enough to give us an idea about the behaviour of halogens and pseudohalogens. - JQ) The hydrogen halides and hydrogen pseudohalides behave as acids. The acids formed by pseudohalogens are relatively weak acids, HN, Hydrazoic acid Pka=4.4 HCN Hydrocyanic acid Pka=8.9 HCl Hydrochloric acid = Pka=— 7.0 (2) The silver and mercurous salts of pscudohalides are-insoluble in water just like corresponding halides. AG) The Pscudohalogens and halogens are volatile compounds and Teact with alkalies in exactly the same manner. (CN); + 20H” === CN-+OCN+H,0 (SCSN,), + 20H” === SCSN, + OSCSN,” +H,0 u C+ 20H” === C1" + 0Cl"+H,0 : . fo) Both pseudohalogens and halogens form addition compounds with * unsaturated organic molecules, CH, = CH, + (SCN), ——+ C.HSCN), CH.=CH,+Br, ——+ BrH,C —CH:Br[Chapter 16) THE HALOGENS (GROUP VILA) (5) Pseudohalogens combine = with halo, vC vi molecules o form inerhalogen vnc cores ih et Peeedohaogsn CNCI, CNBr, IN, CNBr+NaN, ——+ CN:N,+NaBr (6) Pseudohalides form ions similar to polyhalide ions NHSCN), resembles KI, (7) Lead (IV) salts formed with halogens and pseudokalcgens are covalent in _ Rature and decompose to liberate free halogens and pseudohalogens, | respectively. Pbci, ——> PDC. + Cl, Pb(SCN), ——> Pb(SCN), + (SCN): - CHEMICALS IN WARFARE Modern chemical warfare started with the use of chlorine. Later on, phasgene and mustard gas were used. cy, . C=O . Ci—CH,—CH,, cr. ee Ys Phosgene cl —CH, — CH; (Carbonyl chloride) > + Mustard gas . Organophosphorus nerve gases were later developed. Chemical defoliating and riot control agerts were subsequently developed. The infamous compound 2, 1,5-T or agent Orange is F: oxic,