914 Chemistry of the Main-Group Elements TABLE 21.9 | Uses of Some Sulfur Compounds Compound Use cs: Manufacture of rayon and cellophane Manufacture of CCL, $0, Manufacture of H,S0, Food preservative Textile bleach 1,80, ‘Manufacture of phosphate fertilizers Petroleum refining Manufacture of various chemicals Na,S:05 Photographic fixer Concentrated sulfuric acid is a viscous liquid and a powerful dehydrating agent. “The concentrated acid is also an oxidizing agent. Copper is not dissolved by most acids. E” for Cu?” [Cu is postive, so Cu is not oxidized by H* (H)0"). Iti, how ever, dissolved by hot, concentrated sulfuric acid. In this reaction, sulfate ion in acid solution is reduced to sulfur dioxide: Cu(s) + 2H,80,{1) —> CuSO4(ag) + 2H,0() + S068) More sulfuric acid is made than any other industrial chemical. Most of this acid is, used {o make soluble phosphate and ammonium sulfate fertilizers. Sulfuric acid is also used in petroleum refining and in the manufacture of many chemicals. Table 21.9 lists, uses of some sulfur compounds, Group VIIA: The Halogens ‘The Group VIIA elements, called the halogens, have very similar properties, or at least they have properties that change smoothly in progressing down the column. All are reactive nonmetals, except perhaps for astatine, whose chemistry is not well known, ‘As a sccond-period clement, fluorine does exhibit some differences from the other cle~ ments of Group VIIA, although these are not so pronounced as those of the second-period ‘elements in Groups IIA to VIA. The solubilities of the fluorides in water, for example, are oflen quite different from those of the chlorides, bromides, and iodides. Caleium chlo ride, bromide, and iodide are very soluble in water. Calcium fluoride, however, is insol- uble. Silver chloride, bromide, and iodide are insoluble, but silver fluoride is soluble. ‘Al of the halogens form stable compounds in which the element is in the —1 oxi dation state. In fluorine compounds, this is the only oxidation state. Chlorine, bromine, and iodine also have compounds in which the halogen is in one of the positive oxi- dation states +1, +3, +5, or +7. The higher positive oxidation states (> +1) are ‘due to the involvement of d orbitals in bonding. Chlorine Chlorine gas, Cla, was discovered in 1774 by the Swedish chemist Karl Wilhelm Scheele by heating hydrochloric acid with manganese dioxide, 411Cl(ag) + MnO,(s) —+ MaCly(ag) + Chale) + 2H,0(0 He immediately noted the suffocating odor of the gas. Scheele also discovered that chlorine solutions could bleach cotton cloth, Within a few decades, chlorine-based| see the introduction to Chapter 2. The electrolysis of aqueous sodium chloride is discussed in Section 19.10, FIGURE 21.59 A ‘The hydrogen chloride fountain The flask contains hydrogen chloride gs. When water is added tothe flask fom the cropper, the hycrogen chloride sss of redung te pressure in the ask ‘mosphere pressure pushes the wae in the beaks inca te ls, forming seem fountain. Water inthe beaker has bromiymot blue inate in it The ecto soluion inthe fas yellow becuse it is acd 24.11 Group VIIA: The Halogens 915 bleaches became major items of commerce. Currently, chlorine is the most commer: cially important halogen, Properties of Chlorine Chlorine gas has a pale greenish yellow color. It is a very reactive oxidizing agent and supports the combustion of many substances in a manner similar to oxygen. We discussed the reaction of chlorine with sodium in Chapter 2, < All of the halogens are oxidizing agents, though the oxidizing power decreases from fluorine to iodine. Thus, chlorine is stronger oxidizing agent than either bromine or iodine, When chlorine gas is bubbled into a bromide solution, free bromine is obtained. Similarly, chlorine oxidizes iodide ion to iodine Ch(@) + 2KBr(ag) —+ 2KCllag) + Bralag) Ch{@) + 2KIag) —+ 2KClag) + (aq) ‘These reactions can be used as a test for bromide and iodide ions, Suppose an aque fous solution of chlorine is added to a test tube containing cither bromide or iodide ion. The corresponding free halogen is formed in the water solution, It is readily iden- tified by adding the organic solvent methylene chloride, CH3Cls, which dissolves the halogen, forming a colored layer at the bottom of the test tube. Bromide ion gives an lorange layer; iodide ion gives a violet layer. OF course, neither bromine nor iodine is strong enough to oxidize chloride ion, Chlorine reacts with water by being both oxidized and reduced: Cle) + 1,00) = HCIO(ag) + HCKag) In an aqueous solution of chlorine at 25°C, about two-thirds of the chlorine is pres. ent as Clx(aq); the rest is HCIO and HCl. Preparation and Uses of Chlorine Chlorine is a major industrial chemical. It is prepared commercially by the electrolysis of aqueous sodium chloride. < Chlorine can be prepared in small amounts for laboratory use by the reaction of chloride ion with a strong oxidizing agent, such as potassium dichromate or manganese dioxide. How. ever, chlorine is readily available in steel cylinders for laboratory work. ‘The principal use of chlorine is in the preparation of chlorinated hydrocarbons, such as vinyl chloride, CH:—=CHC! (for polyvinyl chloride plastics), and methyl chlo- ride, CHCl (for the manufacture of silicones, polymers with SiO bonds and organic groups). Various insecticides are also chlorinated hydrocarbons; many of these (such as DDT) are now restricted in their use because of possible environmental damage. Other major uses of chlorine are as a bleaching agent for textiles and paper pulp and as a disinfectant. Not long after the discovery of chlorine, chlorine bleaches became avail- able commercially. Chlorine solutions were used as disinfectants early in the nineteenth century. Today, chlorine gas is commonly used for disinfecting municipal water supplies. Hydrogen Chloride Hydrogen chloride, HCI, is a colorless gas with a sharp, pen- etrating odor. The gas is very soluble in water (Figure 21.59), and the water solution is commonly referred to as hydrochloric acid. The molecular species HCl ionizes nearly completely in aqueous solution: HOU) + HO) —> HO" (aq) + Cas) Hydrogen chloride can be produced by heating sodium chloride with concentrated sulfuric acid NaCl) + H,80,() 2+ NaHSO,(5) + HCI) On stronger heating, the sodium hydrogen sulfate reacts with sodium chloride to pro- duce additional hydrogen chloride acs) + ‘aHSO,(s) + NaySO«(s) + HC)916 Chemistry of the Main-Group Elements \GURE 21.60 > ‘he action of concentrated sulturic aid on halide salts Concentated suc ac was added to wath asses contning fom et igh, NaCl Net, and Nal. ie the formation of some Bin the center watch ls (brow) and the famton of ep0" (pul) over the wate ls onthe nh. These halogens form when concerted suture aid nies the caesponding baie ions, Choi ion nt oxidized by H5S0. Hydrogen bromide and hydrogen iodide can also be produced from their salts by a similar replacement reaction, but in these cases phosphoric acid is used instead of sulfuric acid, which tends to oxidize the bromide and iodide ions to the respective clements Figure 21.60) ‘Most of the hydrogen chloride available commercially is obtained as a by-product in the manufacture of chlorinated hydrocarbons. In these reactions, hydrogen bonded to carbon is replaced by chlorine, forming the chlorinated compound and HCI, An ‘example is the preparation of methyl chloride, CHCl, from methane CHg) + Clie) —> CHCl) + HCI) Hydrochloric acid is the fourth most important industrial acid (afler sulfuric, phos- phoric, and nitric acids). It is used to clean metal surfaces of oxides (a process called pickling) and to extract certain metal ores, such as those of tungsten. Oxoacids of Chlorine The halogens form a variety of oxoacids (Table 21.10). Figure 21.61 shows the structures of the chlorine oxoacids. The acidic character of these acids increases with the number of oxygen atoms bonded to the halogen atom—that is, im the order HCIO, HCIO3, HCIOs, HCIO,, (See Section 15.5 for a discussion of ‘molecular structure and acid strength.) Perchloric acid, HCIO,, is the strongest of the ‘common acids, OF the chlorine oxoacids, only perchloric acid is stable; the other ‘oxoacids have never been isolated and are known only in aqueous solution Hypochlorous acid, HCIO, is produced when chlorine disproportionates (is oxidized and reduced) in water. In basic solution, the equilibrium is very far toward the acid anions: Cl(g) + 20H™(ag) — CI™(ag) + CIO (ag) + HO) dation Purine Chlorine Bromine Jodine General State Oxoacids Oxoacids Oroacids Oxoacids Name +1 HEO* HCIOt HB:Ot HOF Hypohalous acid 43 = HCI0,+ HB:0;+ = Halous acid +5 = HCIOs+ HBrOst HIO, Halic acid 47 = HCIO, HB:O,¢ HO, Pethalic acid H1O, ‘Te oxidntion sate of Fin HFO is ~1 ‘Those aids are known ely st agueous solution,24.11 Group VIIA: The Halogens 917 Oe ay oay aby HCW FIGURE 21.61 A. ‘Structures of the chlorine oxoacids The modes ofthe cxoaids ao include ais on the G atom, FIGURE 21.62 A Solution of sodium hypochoste bleach “he solution is manufactured by abowing iorne and sodium hyde solution (om the lecr\ys of equeous sodium cord) to rea. HCW, HCW, Ha, Solutions of sodium hypochlorite are manufactured by allowing the chlorine gas released by the electrolysis of aqueous sodium chloride to mix with the cold solution of sodium hydroxide that is also obtained in the electrolysis, These solutions are sold asa bleach (Figure 21.62). Hypochlorite ion itself is unstable, disproportionating into chlorate ion, C1037, and chloride ion, 3C1O™(ag) — C10s“(ag) + 2C-(ag) At room temperature the reaction is slow; but in hot solution in the presence of base, the reaction is fast. Therefore, when chlorine reacts with hot sodium hydroxide solu- tion, sodium chlorate is the product instead of sodium hypochlorite, 3CI,(g) + 6NaOH(ag) —+ NaClOs(ag) + SNaCK(aq) + 300) Sodium chlorate can be crystallized from the solution. Solutions of chloric acid, HCIOs, can be prepared, although the pure acid cannot be isolated, Sodium perchlorate and potassium perchlorate are produced commercially by the electrolysis of a saturated solution of the corresponding chlorate, The anode reaction is (aq) + 3H,0) — ClO,"(aq) + 2x0" (ag) + 26° Hydrogen evolves at the cathode. Perchloric acid can be prepared by treating a per- chlorate salt with sulfuric acid, KCIO,(s) + H>SO\() —> KHSOA(s) + HCIO,() ‘The perchloric acid is distilled from the mixture at reduced pressure (to keep the tem: perature below 92°C, where perchloric acid decomposes explosively), ‘Table 21.11 lists uses of some halogen compounds. TABLE 21.11 | Uses of Some Halogen Compounds Compound Use AgBr, Agl Photographic film cc Manufacture of fluorocarbon HBr Pesticide CHCl, Manufacture of vinyl chloride (plastics) HCL Metal treating Food processing Nacio Houschold bleach, Manufacture of hydrazine for rocket fuel NaCiOs Paper pulp bleaching (with CIOs) KI Human nutritional and animal feed supplement