Fluorine F [Hel 2s? 2ps =I ~ : Chlorine Cl [Ne] 3s*3pS —1 +1+I +1V+V+VI+VIL Bromine Br [Ar] 3d 4s4p* —1+1+I1+1V+V +V1/ Todine 1 [Kr] 4d! Ss?Sp$ 14141 = +V + VID Astatine At [Xe] 4f¥ Sd! 6s? 6ps : * See p. 154. Electronic Structure and Oxidation States The halogens show very close group similarities. The elements all electrons in their outer shell, and they either gain an electron by fe ionic bond (giving X~) or form a covalent bond, in order to comp “always has the oxidation number (—I). Among the other - numbers of (+1), (+IIT), (+V) and (+VII) are possible. states arise quite logically by unpairing electrons, that is from filled p and s levels to empty d levels, and exam _ interhalogens and halogen oxides. The oxidation Scanned with CamScannerHsI0, Basic solution Oxidation states +vil + +i +! O33 * | 066 ————— oc: ———4, (0. ———c0, > 036 10, cl 050 088 Oxidation states =i + Scanned with CamScannerwith Cl,, Br, and I, (Table 5.16). The bond. energy in F, (159 kJ mol!) because of repulsion between non-bonding ele largely responsible for the high reactively of fluorine. In Cl,, Br, the possibility of multiple bonding involving d orbitals. The fonization energies of the halogens are all very high, which that there is little tendency to lose electrons. The value for F is highest, since eleetrons are firmly ted in small atom and the ionization energy of 1s lower because Iisa larger atom (see Table 5.16). ” Tape 5.16 Mp. Bop. Heat of First Electron Hydration dissociation _ ionization affinity energy X orbondenergy energy energy °C ac kJ mol"! kJ mol"! kJ molt kJ mol“! F, -220 —188 159 1681 —333 ~315 ci, -101 35 243 1255 —348 -381 Br, 7 $8 193 1142 324 347 oon i4 183 151 1191 -295 —305 However, the first ionization energies of Cl, Br and I are lower than the value for H of 1311 kJ mol. The reason why H+ exists but no simple X* ions are formed is that H* is very small and the ionization energy is recovered in the form of a high lattice energy, or a high hydration energy, whereas the X* ions. are large and consequently have low hydration and lattice energies. A few com- pounds are known where I* is stabilized by forming a complex with a Lewis base, for example [I(pyridine), }+ NO,-, and these are discussed under Basie ~ properties of the halogens. The halogen molecules are all coloured. This is due to the absorption fisible light, which results in the excitation of outer electrons to hig The excitation energies follow the same trend as the ioniz ‘is excitation of the small F atom requires a large no ie larger I atom requires less energy. Ga ae) and therefore | Scanned with CamScannerFor fluorine and chlorine which are gaseous at room temperature, the heats of fusion and evaporation are omitted and their oxidation potential depends only = ‘on the sum of the heat of dissociation, electron affinity, and heat of hydration. (The heats of fusion, evaporation and dissociation are positive because energy must be supplied.) Thus despite the electron affinity of chlorine being highest (see Table 5.17) F is the strongest oxidizing agent because it has the largest Taste 5.17. Enthalpy (AH) Values for 4X, + Xoyyersta (all values in kJ mol!) * 4 theat Jheat fheat Electron Heat of Sum fusion evaporation dissociation affinity _—_—ihydration j F, = = +159/2 ~333 sis -768 | ei, = vas +243/2 348 381 607 | / Br, +31/2 +193/2 —324 —347 559 I, +15/2°+44/2 +151/2 295 -305 -390 negative AH value in the energy cycle. This is largely because of its low heat of dissociation and high heat of hydration. F is an extremely strong oxi agent, and it will replace Cl- in solution and even when dry. Similarly, chlorine gas will displace Br~ from solution and this fact is used in the preparation of bromine. In general any halogen of low atomic number will oxidize halide ions of higher atomic numb: The decrease in oxidizing power on descending Group VII is illustrated by the reaction of the halogens with water. Fluorine is so strong an oxidizing ag¢ that it oxidizes water to oxygen. The large negative free energy change i __ ates a strongly exothermic and spontaneous reaction. Fy 4 H,O-2H1+2F +40, AG= Scanned with CamScannerReactivity of the Elements Fluorine is the most reactive of all the elements in the Periodic table (refs. and 47). It reacts with all the other elements except the noble gases He, Ne and Ar. The reactivity of the halogens decreases with increased atomic number. Chlorine and bromine react with most of the elements, though less vigorously, whilst iodine is less reactive and does not: combine with some ele- ments such as $ and Se. Fluorine and chlorine frequently oxidize elements further than bromine and iodine, thus they bring out higher valencies, for: example PBr,, PCl,, SbF,, and'S,Br,,SCl, and SF,. The great reactivity of fluorine is due to the low energy of the F-F bond, the extremely high oxidizing power, the small size of the atoms or ions and the high Covalent radius Ionic radius ¥- Pauling’ Abundance in electronegativity earth's crust A A F 0-72 1:36 4.0 900 cl 0-99 1-81 3.0 314" Br 1d 1.96 2.8 1-6 i 1-33 219 2-5 0-3 * Abundance of chlorine is 15 000 p.p.m. in sea water. electronegativity. The small size of the ions results in a high coordination num- Ber, and hence a high lattice energy in the crystal. The high electronegativity results in the formation of very strong bonds with most other elements. Separation and Uses of the Elements . ‘a The main source of fluorine is the mineral fluorspar, CaF,. This | ion and anhydrous HF. Fluorine is then obtained by ; and HF at 100°C. Tis Scanned with CamScannercurrent being needed, more heat being produced, and eventually xplo To prevent this from happening, coke impregnated with copper is used ¢ anode. Production of fluorine first became important when it was discovered that the isotopes of uranium could be separated by gaseous diffusion of UF, which is made: U or UO, + HF + UF, UF, + F, + UF, or UF, + CIF; + UF, Because the F-F bond is so weak, and atomic fluorine is a highly exothermic oxidizing agent, fluorine can be used as a rocket fuel. ; Chlorine is produced in large quantities by the electrolysis of aqueous NaCl solutions in the manufacture of NaOH, and of fused NaCl in the manufacture of sodium. Before 1960 chlorine was a by-product from these processes, but | with the great increase in the use of chlorine in the manufacture of plastics such ' as polyvinyl chloride, chlorine is now the major product. | electrolyse 2Nacl+2H,0 ““""*, NaOH + Cl, +2H, | oNacr. CSE, ona cy At one time, chlorine was produced by the Deacon process, but this became obsolete because at the high temperature required by the catalyst, the equilib- rium lies to the left, and the process is uneconomic. CuCl, catalyst 2HCIl+4o, —————_ H,0+ Cl, 400-450 °C However, HCl is now available as a by-product (e.g. from the pyrolysis of ethylene dichloride to vinyl chloride) and improved catalysts which are active as low as 200 °C have been found (CuCl,/AICI, catalyst with FeCl, as pro- moter) so the process is again in use. About half a million tons of chlorine are produced annually in the UK. Ov ree quarters of this is used to make organic compounds: a chlorides; perchloro and dichloro ethylene; ethylene Scanned with CamScannerCl, + 2Br- The bromine is absorbed in Na,CO, NaBrO,, which when acidified and HBrO, + SHBr~ 3Br, + 3H,O Over 50 000 tons of bromine are produced annually in the USA, and 80% of this is used to make ethylene dibromide which is added to motor fuels to act as a lead scavenger. Other uses include the production of AgBr used for photographic purposes, organic derivatives such as methyl bromide, ethyl bromide, butyl bromide and dyestuffs. Todine is obtained from Chile saltpetre, which is mainly NaNO,, but eon- | tains traces of sodium iodate and sodium periodate. The iodate concentrate is | reduced to iodine by NaHSO,. 210,- + SHSO,~ + 3HSO,- + 2802-+ H,0 +1, Silver iodide is used for photographic films, and potassium iodide is used in animal feeds, for medical purposes, and for making iodoform CHI, and methyl iodide CHI. " Astatine does not occur in nature. Twenty artificial isotopes have been made, all of which are radioactive. The most stable isotopes are !°At and MAt with half-life periods of 8-3 hours and 7-5 hours respectively. The latter has been made by bombarding bismuth with high-energy o-particles. an { rei 27, rat The chemistry of "'At has been studied by tracer methods using minute quan- tities (10-4 mole). It decays by orbital electron capture and by a-emission, and appears to resemble iodine quite closely. Tydrogen Halides HX halogens all react with hydrogen and form hydrides n of hydrogen with fluorine is quite violent, the re x Eatemiperatire, and luatroteag r Scanned with CamScannerie Anhydrous HF is a catalyst for making long-chain alkylbenzenes which are subsequently converted to sulphonates and used as detergents. Aqueous HF is used for etching glass, pickling steel and making many fluorides such as AIF, and BF,. ‘ ; Al,O, + 6HF + 2AIF, + 3H,0 aH0, 3,0, +6HF —“+ 2BF, + 3H,S0,.H,0 the AIF; is used mainly for adding to Al,O, in the electrolytic extraction of aluminium. NH,C1 is generally used to make HCl in the laboratory, because | the resultant NH,HSO, is soluble, and the reaction proceeds smoothly; however, NaClis used in industry because it is cheaper. NH,CI + H,SO, + NH,HSO, + HCI NaCl + H,S0, + NaHSO, + HCI Productiqn of HC! in the UK is about 200 000 tons a year. HBr and HI are not made from the reaction between sulphuric acid and bromides or iodides since the sulphuric acid oxidizes them to Br, and I,. HBr can be produced by the action of H,PO, on a bromide, but in the laboratory the usual method is to add bromine to a mixture of red phosphorus and water. 2P + 3Br, + 2PBr, PBr, + 3H,0 +H,PO, ~3HBr Ina similar way. HI can be made by adding water to phosphorus and i HCI HBr and HI are gases, but HF is a liquid with a boiling dly high boiling point of HF is due to hydrogen’ z Mee 4p Scanned with CamScannerr Rial In ed, but HCl, HBr and HI are completely i ‘ing solvents such as methanol, ionization is much less com ionized than HI. Thus HI is the strongest acid, followed ty HBr anc HF is the weakest. It is at first surprising that though HF has a greater e negativity difference and more ionic character than the other hydrides, it weakest acid in water. Acidic strength is the tendency of HXyurseu ~ Hiyaracesy + Xyeraeay~ This may be represented in stages: dissociation, ion- = ization and hydration. ht. dehydration ,,, ht. dissociation HX inyarated) _— Higas) + Xiqasi Acid, | tonization Electron strength energy afin Werte) Kinyarte) Migas) Xian f ht. hydration t The acid strength is equal to the sum of all the energy terms round thes energy cycle above. acid strength = ht. dehydration + ht. dissociation + ionization energy + electron. affinity + ht. hydration If the various thermodynamic terms are considered in more detail the factors which make HF the weakest halogen acid in water become apparent. The dis- sociation constant k for the change HX yacaeay * Hyarteay +X Grydrteed is given by the equation AG =-RTInk (where G is the Gibbs free energy, R the gas constant and T the srature). However, AG depends on the change in enthalpy AH a1 AS Scanned with CamScannerIonization Electron Energy of H affinity of X —333 348 324 Heat of hydration He —1091 =1091 —1091 —1091 x —515 —381 —347 —305 Scanned with CamScanneree e of heat. ‘ m he ‘anomalous’ value for HF is the result of several _ H-F bond is much stronger than the H-Cl, H—Br or H-I bo their heats of dissociation, Thus it takes nearly twice as much ene ciate HF as is required to dissociate HI. (The strength of the HF shown by the short bond length of 1-0 A compared with 1-7 A in HI. the heat of dehydration for the step HX ydraea) * HX teas) 18 much HE than for the others. This is largely due to the strong hydrogen bonding which occurs in aqueous HF solutions. The unexpectedly low value for the Glectron affinity of F~ also contributes, but the very high heat of hydration of F- is not enough to offset these other terms. By making allowance for the TAS term the corresponding AG values are ob- tained, and from these the dissociation constants are obtained: HF & ion HCI &— 108, HBr k = 10°° and Hi k = 10", From these itis plain that HF is only very slightly ionized in water (that is it is a weak acid), whilst the others are almost totally dissociated (that is they are strong acids). Liquid HF has been used as a non-aqueous solvent. It undergoes self ion- ization: 2HF = H,F* + F Acid-base reactions occur in this solvent system, but few substances act as ‘acids because of the strong proton-donating properties of HF. Mineral acids dissolved in HF do not behave as acids, except for perchloric acid. Many com= pounds react with HIF, and this therefore limits its use as a solvent, though itis, ‘A useful medium for preparing fluoro complexes and fluorides. Halogen Oxides (ref. 48) Most of the halogen oxides are unstable, and tend to explode when subj to shock, or sometimes even with light. The iodine oxides are the most then the chlorine oxides, and the bromine ‘oxides all decompose below ro oxidation states are more stable than the covalent because of the small differenc Scanned with CamScanner6510 mF, th OP, and X,0. oe, BW sibidel ac nib Be is a strong oxidizing agent and reacts vigourously with hhalogens, giving fluorides and oxides. It is formed by passing (2%) NaOH. 2F, + 2NaQH + 2NaF + H,0 + OF; 1,0 is a pas and Br,O is a liquid, and they are both prepared by heating — freshly precipitated mercuric oxide with the halogen gas. 2c, + 2Hgo 22°S. HgCl,.Hg0 + C1,0 They are both coloured and explode in the presence of reducing agents, or on heating. OF, dissolves in water and gives a neutral solution, and with NaOH it gives fluoride ions and oxygen. It is not an acid anhydride. C1, dissolves in water and forms hypochlorous acid HOCI. With NaOH, Cl,0 and Br,O form hypochlorites and hypobromites. These oxides are thus acidic. The oxides may further oxidize these products. NaOBr ~ NaBrO, hypobromite bromate Alll three oxides have structures related to a tetrahedron with two positions o¢- cupied by lone pairs of electrons. 2s 2p Blectronic structure of oxygen TF] PTF atoms—ground state ——— two unpaired electrons form bonds to two halogen atoms—sp’ hybridization—tetrahedral with two lone pairs The bond angle in F,O (Fig. 5.41) is reduced from the tetrahedral "109° 28’ to 105° because of repulsion between the lone pairs, but i Scanned with CamScannerexcept that the O-O bond length of 1-22 A is short compared H,0,. The O-F bond lengths of 1-58 A are much longer than in OF,. C made in a similar way, and apparently contains a chain of four oxygen O,F, and O,F, have been reported, but earlier reports of O,F, have now disproved. XO,. Chlorine dioxide ClO, is a yellow gas which can be condensed to a red liquid, B-pt. TT °C. Tris a powerful oxidizing and chlorinating agent and is used in large quantities for water purification. It is a good bleach and is used to bleach cellulose. It is thirty times as effective as chlorine in bleaching flour. It is also used to manufacture sodium chlorite NaClO,, which is also used for bleaching textiles and paper. 2C10, + 2NaOH + H,O, + 2NaCI0, + 0, + 2H,0 CIO, reacts with water and alkali to form chlorites and chlorates, and is thus a mixed anhydride. C10; + 2NaOH ~+ NaClO, + NaClO, + H,0 sodium” sodium chlorite chlorate ClO, gas detonates readily when concentrated above 50 mm partial pressure, and it explodes with reducing agents. Because of this, it is made in situ, and is diluted with air or CO,. The safest preparation is 2NaClO, + (COOH), 22". a1, + 2C0, + (COONa), + 2H,0 sodium oxalic corse vid Commercially the gas is made Scanned with CamScanner‘a strong oxidizing t with grease. Er AAI forms cloeale and eee 1,0, + 2NaOH ~ NaClO, + NaClO, + H,0. chlorate perchlorate 1,0, has no unpaired electrons and is diamagnetic. It is probably in equilib- rium with ClO,, which is an odd electron molecule and is paramagnetic. heat 1,0, BrO, is a white solid and is produced from ozone and bromine, or from oxygen and bromine under the influence of a silent electric discharge. It is an oxidizing agent and gives acidic solutions with water. Formerly it was incorrectly for- mulated Br,O,. It is unstable above —70 °C. Dichlorine heptoxide ClO, is a moderately stable liquid and is the only exo- thermic oxide of chlorine. It is made by dehydrating perchloric acid with phosphorus pentoxide, and with water forms perchloric acid. 210, PLO 2HCIO, =— CI,0; HO Iodine pentoxide 1,0, is a white solid and is the most stable of all the oxides. It is formed by dehydrating iodic acid by heating to 170 °C. 2HIO, + 1,0, + H,0 Heating to 300 °C decomposes 1,0, to the elements. It is the anhydride of jodie acid and is also an oxidizing agent. An important analytical use of 1,0, is in the detection and estimation of carbon monoxide. It oxidizes CO to CO, quantitatively, liberating iodine, which can be titrated with sodium thiosulphate. 1,0, + SCO +5CO, + I, The structure of 1,0, is (Fig. 5.42): ieee szucttire of 140, is (Fig. 5.2) Scanned with CamScannerX03" X04” These are all based on sp? hybridization of the halogen atoms, and because the s and p levels differ appreciably in energy, the sp? hybrid orbitals form fairly| weak o bonds. The stability of these ions is due to strong px-dz bonding be-| tween full 2p orbitals on oxygen with empty d orbitals on the halogen atoms, Fluorine has no d orbitals, and cannot form pr-dz bonds, and for this reason| e forms no oxyacids. Many of the oxyacids are known only in solution| or as salts. xO, _Hypohalous acids HOX. The hypohalous acids HOCI, HOBr and HOI are all weak acids and only exist in aqueous solutions. They can be prepared by . shaking freshly precipitated HgO in water with the appropriate halogen. 2HgO + H,O + 2Cl, + HgO. HgCl, + 2HOCI Hypochlorous acid is the most stable and sodium hypochlorite is used for bleaching cotton fabric. NaOCl is produced commercially by electrolysing brine. Hydrogen is liberated at the cathode thus increasing the concentration of OH- in the solution. By agitating the electrolyte, the chlorine formed at the anode reacts with the hydroxyl ions before it can escape. ge (200 7h anode 1c], + 20H- + OCI + Cl + H,O cathode 2H* —H, _ The halogens Cl,, Br, and I, all dissolve to some extent in X, molecules and X- and OX" ions. a (Xe hydrated) Bal Scanned with CamScanneries tend to disproportionate ocr + cr +Cl0,~ hypochlorite chloride chlorate At room temperature hypochlorites are formed, but in hot water di oC ation is rapid and chlorates are formed. Hypobromites can only be made at 0 °C, and hypoiodites disproportionate rapidly at all temperatures. -Halous acids HXO,. The only halous acid known is chlorous acid HCIO,, This only exists in solution, but it is a stronger acid than HOCI. Chlorites are made from CIO, and either sodium peroxide, or hydrogen peroxide and sodium hydroxide. Chlorites disproportionate on heating to chlorate and | chloride. | 2C10, + Na;0, ~ 2NaClO, + 0; 3NaClO, + 2NaClO, + NaCl Halic acids HXO,. The halic acids HCIO, and HBrO, are known in solution, but iodic acid HIO, exists as a white solid. Thus the stability increases with increased atomic number. The acids are all strong oxidizing agents and strong acids. HIO, can be made by oxidizing iodine with fuming nitric acid. Chiorates are used in fireworks and matches, whilst sodium chlorate is a powerful weed killer. Chlorates may be made by the action of chlorine on hydroxides or by electrolysing hot chloride solutions. It is thought that the hypochlorite first formed in this reaction combines further: 6NaOH + 3Cl, + NaClO, + SNaCl + 3H,0 2HOCI + OC + C1O> + 2H* + 2c The thermal decomposition of chlorates and bromates is complex and is not fully understood. KCIO, may decompose in two different ways. depending on the temperature. 2KCIO, + 2KCI +30, well known experiment to produce oxygen frequently gi well. Zn(CIO,), decomposes to zinc oxide, 03 i ° Scanned with CamScannerPerhalic acids HXO, . Perchloric and periodic acids and their known Perbromates have only recently been prepared by the action o ful oxidizing agents such as XeF, or F;, or electrolytically from Perchloric acid HCIO, is one of the strongest acids, and is a powerful oxid agent which explodes when in contact with organic matter and sometimes on its own. The commercial 70%HCIO, has almost the composition of the dihyd- rate. It can be made from NH,CIO, and dilute nitric acid, or from NaClO, and concentrated hydrochloric acid. NaClO, is made by electrolysing aqueous NaCIO,, using smooth platinum electrodes to give a high oxygen overpotential to prevent the electrolysis of water. Nacio, +H,0 ““, Nacio, +H, Except for the potassium, rubidium, caesium and ammonium salts most perchlorates are very soluble, but the insolubility of KCIO, is used to detect potassium in qualitative analysis. Magnesium perchlorate is very hygroscopic and is used as a drying agent called ‘anhydrone’. The perchlorate ion is tetrahedral. The C1O,~ ion has only a very slight tendency to form complexes with metal ions, and for this reason perchlorates are useful for introducing metal ions to a reaction without the risk of forming unwanted complexes. The common form of periodic acid is HIO,.2H,O or H,1O,. This is ob- tained by passing chlorine into a solution of iodine in NaOH. The salt Na H,1O, so formed is treated with AgNO, giving Ag,1O,, which on treatment with chlorine and water and evaporating with concentrated H,SO, gives H,1O,. When heated, the acid first loses water, polymerizes, and forms an iso- polyacid. More water is lost on further heating, and eventually oxygen is lost giving iodie acid. : f ae . 2H,10, = Hy,0, “2+ 2110, 10°C, 2HI0, #0, paraperiodie > 19 meanest jodie i = acid: Solutions of periodic acid are used to determine the structure of inds by degradative methods, since HIO, splits 1:2 glycols: Scanned with CamScannerThey can all be prepared by direct combination, or by the action of a halogen on a lower interhalogen: the product formed depends on the con- ditions. 200°C Cl, + F; (equal volumes) —“"S 2C1F Cl, +3F, (excess F,) "©, 2c1F, 1, + Cl, li 1,+Cl, id (equimolar) + ICI lid (excess Cl,) + (ICI), Br, + F, (diluted with nitrogen) + BrF, Br, + F, (excess F,) + BrF, There are never more than two different halogens in a. molecule. The bonds are essentially covalent because of the small electronegativity difference, and the melting and boiling points increase as the difference in electronegativity increases. The compounds formed in the AX and AX, groups are those where the electronegativity difference is not too great, The higher valencies AX, and AX, are shown by large atoms such as Br and I associated with small atoms such as F, because itis possible to pack more small atoms round a large one, The intethalogens are generally more reactive than the halogens (except F) | because the A—X bond is weaker than the X-X bond in the halogens. The reac- tions are similar to those of the halogens. Hydrolysis gives halide and oxy- halide ions, the oxyhalide ion being formed from the larger halogen present. arr, #24 sR- + Bro, Stroma ra 22. crs or Iypoiosite 10, Scanned with CamScannerIt also forms addition compounds called polyhalides with alkali hal ‘NaBr + ICI + NaBriCl ICI is used to iodinate organic compounds, though chlorination may oc depending on the conditions. ——+ chlorination ICI vapour salicylic acid IClin nitrobenzene {____, iodination Since the iodine atoms substitute in positions where there is an excess of electrons, it is thought that the attacking species is I*. Conductivity measure- ments and electrolysis show that ICI ionizes about 1%. 2CI = 1+ + ICl, AX, compounds. The interhalogens are all potential non-aqueous, ionizing solvents. Bromine trifluoride BrF, has been used more than the others, largely because it is a liquid at room temperature and because it is a good, but not too violent fluorinating agent. It self-ionizes considerably. 2BrF, = BrF,* + BF Thus substances producing BrF,* ions are acids and BrF, ions are bases in this solvent. The structure of the AX, type of interhalogen molecule is of in- terest. In CIF, Clis the central atom (Fig. 5.43). —_— 3d 3s 3p De pe ltt (UETE Tt ad atom—excited state Taal see three unpaired electrons form bonds with atoms—sp'd hybridization—trigonal bip} positions occupied Scanned with CamScannerT-shaped with bond angles almost 90°. This indicates structure 3. tortion is due to the lone pairs. It is of interest to note that two bond ns the same and different from the third, which is to be expected because a tri- ‘gonal bipyramid is not a regular shape. ICl, disproportionates quite readily in the gaseous state ICl, +ICI + Cl, and in the solid, two T-shaped ICI, molecules join together forming the dimer (ACI,),, which is flat. eye eS AX, compounds. Of the 4X, compounds, BrF, is too reactive to be suitable for preparing fluorides. In IF, vapour, I is the central atom in the molecule (Fig. 5.44), —— 5s Sp Sd Electronic structure of iodine atom—excited tt fit [t t Tt state er eee five unpaired electrons form bonds with five fluorine atoms—sp'd? hybridization—octahedral with one position ‘occupied by lone pair (alternatively described as square-based pyramid) Liquid IF, conducts electricity and self ionizes, 2IF, = IF, + IF Complex salts are formed by heating IF, with alkali halides, KI+1F,+KUIF,) Scanned with CamScannerFig. 5.44 SH Fig. 5.45 4f 7 (Fig, 5.45) and is probably the only known example of a non-transition using three d orbitals for bonding. Ss Sp Sd Fm a ees seven unpaired electrons form bonds with seven fluorine ‘atoms—sp'd" hybridization Electronic structure of jodine atom—excited [t-] state Polyhalides (refs. 49 and 50) s often associate with molecules of halogens or interhalogens and de ions. For example, the solubility of iodine in water is greatly due to the formation of the triiodide Halide ion’ form polyhali increased by the addition of iodide ions, ion I, 1,417 More complex ions such as pentaiodide 1,~, heptaiodide 1, and enneaiodide [gq have also been prepared. The larger polyiodide ions are generally found combined with large metal ions or large complex cations, since this results in ‘a more stable lattice. The direct addition of iodine to the iodide, either with or without a solvent, results in polyhalides such as KI,.H,0, Rbly, NH, {(C,H,),NI, and Rbl,.2CH,. , The Br,~ lon is much less stable than I,~ and only a few unstable Cl” pounds are known. No F,~ compounds are known, presumably b fluorine has no available d orbitals and therefore cannot expand it t “A number of polyhalides are i for example K(ICI,], K{ICl,], Cs{IBrF] and K n metal halides and interhalogens. 4 Scanned with CamScannerhybridization and orbitals used. For example in ct ae cL Fig. 5.46 Structure of Fig. 5.47 Structure of {1CI,J- ion HICL,| ion, (the structure of the [1,]- ion is dif. r ferent), Electronic structure of 777 iE iodine atom—ground state Structure of I having T formedonecovaent [i] (HIRTE] ETT and one coordinate bond in {ICI,I- cates | sp'd? hybridization—trigonal bipyramid with three positions ‘occupied by lone pairs Similarly the structures of the pentahalide ions (ICl,]- and [BrF,]~ are p (see Fig. 5.47). Electronic structure of iodine atom—excited Scanned with CamScanneroperties is less obvious in Group VIL. The incre ions indicates an increasing tendency to basic or metallic cha . emphasized that iodine is not a metal. ‘ Fluorine is the most electronegative element and has no basic (that is, it has no tendency to form positive ions). If CIF has any tende ionize it will form Cl* and F~ due to the greater electronegativity 0 Chlorine shows a slight tendency to form positive ions in this case, and it has an oxidation number of (+1) in HOCI. Positive bromine exists in complexes such as Br(pyridine)NO, and BrF;. These ionize and give (Br pyridine}* and NO,-, and BrF,* and BrF,~ respectively. Positive iodine compounds are more numerous and better established. The evidence for existence of positive iodine as I* and I°* is given below. (1) Evidence for I* ICI conducts electricity when molten. Both 1, and Cl, are liberated at the anode, but only I, at the cathode. The ionization is probably: 2ICl = It + ICl,~ Molten ICN behaves in a similar way, but in pyridine it gives I, only at the cathode. This suggests the more simple type of ionization: ICN = I+ +CN- ICI behaves as an electrophilic iodinating agent, converting acetanilide to 4- iodoacetanilide, and salicylic acid to 3,5-di-iodosalicylic acid. Because the at- tacked sites have an electron excess, the iodine must be positive. If iodine is dis- solved in an inert solvent and passed down a cationic fon exchange column, some iodine is retained in the resin. H¢Resin~ + I, + I*Resin~ + HI positive ion retained may be eluted with KI, to estimat ‘it may be allowed to react with various reagents. _ 2 Scanned with CamScannerMolten ICI, has a high conductivity (8-4 x 10? chm! cm), Because I, and Cl, are liberated at both electrodes, ionization into ICI,* and ICI, is in- dicated. If T, is treated with fuming HNO, and acetic anhydride, I(acetate), is formed. If this is electrolysed using silver electrodes, one equivalent of Agl is formed at the cathode for every three Faradays of electricity passed. This proves ionization: (acetate), = 1°* + 3(acetate-) 7 If I, is oxidized with concentrated HNO, in the presence of acetic anhydride and phosphoric acid, iodine phosphate is formed. 1+ Ac,O + H,PO, + IPO, If this ionizes, I°+ would be expected. Cationic iodine exists in sulphuric acid solutions. Iodine dissolves in dilute oleum and forms 1+, but in more concen- trated oleum I* is formed. ee “hy A few molecules have properties similar to the halogens, and are call pseudohalogens. These include cyanogen (CN),, thiocyanogen (SCN), and selenocyanogen (SeCN),, A number of negative ions such as cyanide CN, ia cyanate OCN-, thiocyanate SCN-, selenocyanate SeCN-, tellurocyanate TeCN-, isocyanate ONC~ and azide N,~ resemble the halide ions to some ex- tent. The'best known example is CN~, which resembles Cl-, Br~ and I in the following respects. (i) Tt forms an acid HCN. (ii) It can be oxidized to form a molecule cyanogen (CN),. Gift) Tt forms insoluble salts with Ag*, Pb?* and Hg*. * (iv) ‘interpscudohalogen’ compounds CICN, BrCN and ICN can - formed. ; AgCN is insoluble in water but soluble in ammonia, like AgCI ‘It forms a large number of complexes similar to halide P= and [CuCl,}?-; [Co(CN),I*and [Co Pseudohalogens and Pseudohalides Scanned with CamScanner