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706

Sulfur

Ch. 15

15.2.6 Oxoacids of sulfur

Sulfur, like nitrogen and phosphorus, forms many oxoacids though few of these can be isolated as the free acid and most are known either as aqueous solutions or as crystalline salts of the corresponding oxoacid anions. Sulfuric acid, H2S04, is the most important of all industrial chemicals and is manufactured on an enormous scale, greater than for any other compound of any element (p. 407). Other compounds, such as thiosulfates, sulfites, disulfites and dithionites, are valuable reducing agents with a wide variety of applications. Nomenclature is somewhat confusing but is summarized in Table 15.18 which also gives an indication of the various oxidation states of S and a schematic representation of the structures. Previously claimed species such as sulfoxylic acid (HzSOz), thiosulfurous acid (H2S202), and their salts are now thought not to exist.

Table 15.19 Some standard reduction potentials of sulfur species (25,pH 0)

Couple
EON

-0.082
+O. 142

0.339 0.449 0.465 0.509 0.564 2.123

Many of the sulfur oxoacids and their salts are connected by oxidation-reduction equilibria: some of the more important standard reduction potentials are summarized in Table 15.19 and displayed in graphic form as a volt-equivalent diagram (p. 435) in Fig. 15.28. By use of the couples in Table 15.19 data for many other oxidation-reduction equilibria can readily be calculated. (Indeed, it is an instructive exercise to check the derivation of the numerical data

Figure 15.28 Volt-equivalent diagram for sulfur-containing species in acid solution.

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Oxoacids of sulfur

707

given in parentheses in Fig. 15.28 from the data given in Table 15.19 and to calculate the standard reduction potentials of other couples, e.g. HS04-/H2S 0.289 V, HS04-/H2S03 0.119 V, H2S03/S2032- 0.433 V, etc.) Several important points emerge which are immediately apparent from inspection of Fig. 15.28. For example, it is clear that, in acid solutions, the gradient between H2S and Sg is less than between Sg and any positive oxidation state, so that H2S is thermodynamically able to reduce any oxoacid of sulfur to the element. Again, as all the intermediate oxoacids lie above the line joining HSO4- and Sg, it follows that all can ultimately disproportionate into sulfuric acid and the element. Similarly, any moderately powerful oxidizing agent should be capable of oxidizing the intermediate oxoacids to sulfuric acid (sometimes with concurrent precipitation of sulfur) though by suitable choice of conditions it is often possible to obtain kinetically stable intermediate oxidation states (e.g. the polythionates with the stable S-S linkages). It follows that all the oxoacids except H2SO4 are moderately strong reducing agents (see below). The formal interrelationship between the various oxoacids of sulfur can also be illustrated in a scheme('86)which places less emphasis on oxidation-reduction reactions but which is useful in suggesting possible alternative synthetic routes
lg6M. SCHMIDTand

to these oxoacids. Thus successive addition of SO3 or SO2 to H20 can be represented by the scheme:

sulfuric

-1 so2
T so3

disulfuric

H2S206 dithionic

sulfurous

disulfurous

Likewise addition of SO3 to H202, H2S and H2S, generates the formulae of the other oxoacids as follows:

It should be emphasized that not all the processes in these schemes represent viable syntheses, and other routes are frequently preferred. The following sections give a fuller discussion of the individual oxoacids and their salts.
Is7R. L. KUCZKOWSKI, R. D. SUENRAM and F. J. LOVAS, J. Am. Chem. Soc. 103, 2561-6 (1981).

W. SIEBERT, Oxyacids of sulfur, Section 2.4 in Comprehensive Inorganic Chemistry, Vol. 2, Chapter 23, pp. 868-98, Pergamon Press, Oxford, 1973.

Table 15.20 Some physical properties of anhydrous H2S04 and D2SO4'")

MPPC BPPC Density(25")/g cm-3 Viscosity(25")/centipoise Dielectric constant E Specific conductivity ~(25")/ohm-'cm-'
10.371 -300 (decomp) 1.8267 24.55 100 1.0439 x 14.35

1.8572 24.88

0.2832 x

fa)Inthe gas phase H2SO4 and DzSO4 adopt the C2 conformation with r(0-H) 97 pm, r(S-OH) 157.4 pm, r(S-0) 142.2 pm; the various interatomic and dihedral angles were also determined and the molecular dipote moment calculated to be 2.73 D.(187)

708

Sulfur

Ch. 15

Industrial Manufacture of Sulfuric Acid

Sulfuric acid is the world's most important industrial chemical and is the cheapest bulk acid available in every country of the world. It was one of the first chemicals to be produced commercially in the USA (by John Harrison, Philadelphia. 1793): in Europe the history of its manufacture goes back even further - by at least two c e n t u r i e ~ . ( ' ~Concentrated ~.~~~) sulfuric acid ("oil of vitriol") was first made by the distillation of "green vitriol", FeSOJ.nH20 and was needed in quantity to make NazSO? from NaCl for use in the Leblanc Process (p. 71). This expensive method was replaced in the early eighteenth century by the burning of sulfur and Chile saltpetre (NaN03) in the necks of large glass vessels containing a little water. The process was patented in 1749 by Joshua Ward (the Quack of Hogarth's Harlot's Progress) though it had been in use for several decades previously in Germany. France and England. The price plumetted 20-fold from 2 to 2 shillings per pound. It dropped by a further factor of I O by 1830 following firstly John Roebuck's replacement (ca. 1755) of the fragile glass jars by lead-chambers of 200ft3 (5.7 m3) capacity, and, secondly, the discovery (by N. Clement and C. B. DCsormes in 1793) that the amount of NaN03 could be substantially reduced by admitting air for the combustion and the process was of sulfur. By 1860 James Muspratt (UK) was using lead chambers of 56000ft3 capacity (1585111~) continuous. The maximum concentration of acid that could be produced by this method was about 78% and until 1870 virtually the only source of oleum was the Nordhausen works (distillation of FeSOi.nH20). Today both processes have been almost entirely replaced by the modern contact process. This derives originally from Peregrine Philips' observation (patented in 1831) that SO2 can be oxidized to SO3 by air in the presence of a platinum catalyst. The modern process uses a potassium-sulfate-promoted vanadium(V) oxide catalyst on a silica or kieselguhr support.(lm) The SO2 is obtained either by burning pure sulfur or by roasting sulfide minerals (p. 651) notably iron pyrite, or ores of Cu, Ni and Zn during the production of these metals. On a worldwide basis about 65% of the SO2 comes from the burning of sulfur and some 35% by the roasting of sulfide ores but in some countries (e.g. the UK) over 95% comes from the former. The oxidation of SO2 to SO3 is exothermic and revcrsible:
SO2

SO3:

AH" - 98 W mol-'

According to le Chatelier's principle the yield of SO3 will increase with increase in pressure, increase in excess 0 2 concentration, and removal of SO3 from the reaction zone: each of these factors will also increase the rate of conversion somewhat (by the law of mass action). Reaction rate will also increase substantially with increase in temperature but this will simultaneously decrease the yield of the exothermic forward reaction. Accordingly, a catalyst is required to accelerate the reaction without diminishing the yield. Optimum conditions involve an equimolar feed of 02/SO? (Le. air/SOz:5/1) and a 4-stage catalytic converter operating at the temperatures shown in the Figure.('23)(The V2O.s catalyst is inactive below 400C and breaks down above 620C; it is dispersed as a thin film of molten salt on the catalyst support.) Such a converter may be 13 m high, 9 m in diameter, contain 80 tonnes of catalyst pellets and produce 500 tonnes per day of acid. The gas temperature rises during passage through the catalyst bed and is recooled by passage through external heat-exchanger loops between the first three stages. In the most modern "double-absorption" plants (IPA) the SO1 is removed at this stage before the residual S 0 2 / 0 2 is passed through a fourth catalyst bed for final conversion. The SO3 gas cannot be absorbed directly in water because it would first come into contact with the water-vapour above the absorbant and so produce a stable mist of fine droplets of H2SO4 which would then pass right through the absorber and out into the atmosphere. Instead. absorption is effected by 98% H2SO4 in ceramic-packed towers and sufficient water is added to the circulating acid to maintain the required concentration. Commercial conc HrSOj is generally 96-98% to prevent undesirable solidification of the product. The main construction materials of the sulfur burner, catalytic converter. absorption towers and ducting are mild steel and stainless steel, and the major impurity in the acid is therefore Fe" (IOppm) together with traces of SO? and NO.,. Some idea of the accelerating demand for sulfuric acid can be gained from the following UK production figures: Year io3 tonnes I860 1-60 1870 560 1880 900 I890 870 1900 I100 1917
1400

1960 2750

1980 4750

IXxT. K. DERRY and T. I. WIL.I.IAMS, A Short History of Technology from the Earliest Times to AD 1900, pp. 268, and 534-5, Oxford University Press, Oxford, 1960. The Chemical Industry During the Nineteenth Century, Oxford University Press, Oxford, 1958, 292 pp; IxqL. F. HABER. L. F. HARER. The Chrrniccrl Industp 1900-1930, Oxford University Press, Oxford, 1971, 452 pp. '""A. PHII.I.IPS, in R. THOMPSON (ed.). The Mudern Inorganic Chemicals Industry, pp. 183-200, The Chemical Society, London, 1977. See also W. BUCHNER, R. SCHLIEBS, G. WINTER and K. H. BUCHEL, Industrial Inorganic Chemist?, VCH Publishers, New York. pp. 108-20 (1989).

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Oxoacids of sulfur

709

710

Sulfur

Ch. 15

Sulfuric acid, H2S04

Anhydrous sulfuric acid is a dense, viscous liquid which is readily miscible with water in all proportions: the reaction is extremely exothermic (-880kJmol-' at infinite dilution) and can result in explosive spattering of the mixture if the water is added to the acid; it is therefore important always to use the reverse order and add the acid to the water, slowly and with stirring. The large-scale preparation of sulfuric acid is a major industry in most countries and is described in the preceding Panel. Some physical properties of anhydrous H2SO4 (and D2S04) are in Table 15.20 (p. 707).(191,192) In addition, several congruently melting hydrates,

H2S04.nH20, are known with n = 1, 2, 3, 4 (mps 8.5", -39.5", -36.4' and -28.3", respectively). Other compounds in the H2O/S03 system are H2S207 (mp 36") and H2S4013 (mp 4"). Anhydrous H2SO4 is a remarkable compound with an unusually high dielectric constant, and a very high electrical conductivity which results from the ionic self-dissociation (autoprotolysis) of the compound coupled with a proton-switch mechanism for the rapid
R. J. GILLESPE and E. A. ROBINSON,Sulfuric acid, Chap. 4 in T. C. WADDINGTON (ed.), Nonaqueous Solvent Systems, pp. 117-210, Academic Press, London, 1965. A definitive review with some 250 references. 192N, N. GREENWOOD and A. THOMPSON, J. Chem. SOC. 3474-84 (1959).
I9l

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Oxoacids of sulfur

711

conduction of current through the viscous H-bonded liquid. For example, at 25" the singleion conductances for H3S04+ and HS04- are 220 and 150 respectively, whereas those for Na+ and K ' which are viscosity-controlled are only 3 -5. Anhydrous H2SO4 thus has many features in common with anhydrous H3P04 (p. 518) but the equilibria are reached much more rapidly (almost instantaneously) in H2S04: 2~2S04

concentration of the self-dissociation products in H2S04 and DzS04 at 25" (expressed in millimoles of solute per kg solvent) are:
HSQ- H3S04+ H30' 15.0 11.3 8.0 HS207- H2S207 H20 Total 4.4 3.6 0.1 42.4

+H3S04+ + HS04-

K,(25") = [H3SO4+][HSO4-] = 2.7 x

This value is compared with those for other acids and protonic liquids in Table 15.21:(19') the extent of autoprotolysis in H2SO4 is greater than that in water by a factor of more than 10" and is exceeded only by anhydrous H3P04 and [HBF3(OH)] (p. 198). In addition to autoprotolysis, HzSO4 undergoes ionic selfdehydration:
2H2S04 H30'

+ HS207-;

K,,j(25")5.1 x

This arises from the primary dissociation of H2SO4 into H2O and SO3 which then react with further H2SO4 as follows: H20

As the molecular weight of H2SO4 is 98.078 it follows that 1 kg contains 10.196 mol; hence the predominant ions are present to the extent of about 1 millimole per mole of H2SO4 and the total concentration of species in equilibrium with the parent acid is 4.16 millimole per mole. Many of the physical and chemical properties of anhydrous H2SO4 as a nonaqueous solvent stem from these equilibria. In the sulfuric acid solvent system, compounds that enhance the concentration of the solvo-cation HS04- will behave as bases and those that give rise to H3SO4+ will behave as acids (p. 425). Basic solutions can be formed in several ways of which the following examples are typical:
(a) Dissolution of metal hydrogen sulfates:

+ H2S04 ___\ H30' + HS04-;

K ~ , o ( 2 5 " )= [H30+][HSO4-]/[H20]

so3 +
H2S207
KH2S207

a HzSz07
H3S04'

(b) Solvolysis of salts of acids that are weaker than H2SO4:

KN03

+ HS207-i
= 1.4 x

(250) = ~ H ~ S O ~ ~ ~ ~ H S ~ O

+ H2S04 ----+ K+ + HS04- + HN03 ---+ N&' + HS04NbC104 + ~ ~ ~ / ~ H ~ s ~ o ~ ~ + HC104

H20

It is clear that "pure" anhydrous sulfuric acid, far from being a single substance in the bulk liquid phase, comprises a dynamic equilibrium involving at least seven well-defined species. The

(c) Protonation of compounds with lone-pairs of electrons:

+ Me2CO + H2S04
- log K,
6.2 9.7 12.6 18.9

---+ H30'

+ HS04Me2COH' + HS04- log K,

12 14.0 14.8 29.8

Table 15.21 Autoprotolysis constants at 25"

Compound HBF3(0H) H3P04 H2S04

- log K,
-1 -2 3.6 4.3

Compound HCO;?H HF MeC02H EtOH

Compound H202 H20 D20 NH3

712

MeCOOH + H2S04

(d) Dehydration reactions: HN03 + 2H2S04

Sulfur

Ch. 15

MeC(OH),+

+ HS04-

(d) metathesis between a soluble sulfate and a soluble salt of the metal whose (insoluble) sulfate is required (e.g. BaS04); (e) oxidation of metal sulfides or sulfites. The sulfate ion is tetrahedral (S-0 149pm) and can act as a monodentate, bidentate (chelating) or bridging ligand. Examples are in Fig. 15.29. Vibrational spectroscopy is a useful diagnostic, as the progressive reduction in local symmetry of the SO4 group from T d to C3v and eventually czv increases the number of infrared active modes from 2 to 6 and 8 respectively, and the number of Raman active modes from 4 to 6 and 9.(193) (The effects of crystal symmetry and the overlapping of bands complicates the analysis but correct assignments are frequently still possible.) Pairs of corner-shared SO4 tetrahedra are found in the disulfates, S2O7'- (S-0,-S 124", S-0, 164.5pm, S-0, 144pm); they are made by thermal dehydration of MHS04. Likewise the trisulfate ion S3OIo2- is known and also the pentasulfate ion, SsO& whose structure indicates an alternation of S -0 interatomic distances and very long 0-S distances to the almost planar terminal SO3 groups:

N02'

N205 + 3H~S04 --+

2N02'

+ H30' + 2HS04+ H30' + 3HS04-

The reaction with HN03 is quantitative, and the presence of large concentrations of the nitronium ion, N02+, in solutions of HNO3, MNO3 and N205 in H2S04 enable a detailed interpretation to be given of the nitration of aromatic hydrocarbons by these solutions. Because of the high acidity of H2SO4 itself, bases form the largest class of electrolytes and only few acids (proton donors) are known in this solvent system. As noted above, H2S2O7 acts as a proton donor to H2SO4 and HS03F is also a weak acid: HS03F

+ H2SO4 _1H3S04' + SO3F-

One of the few strong acids is tetra(hydrogen su1fato)boric acid HB(HS04)4; solutions of this can be obtained by dissolving boric acid in oleum: B(OH)3

+ 3H2S207 --+

H3S04'

+ [B(HS04)41- + H2S04
Other strong acids are H2Sn(HS04)6 and H*Pb(HS04)6. Sulfuric acid forms salts (sulfates and hydrogen sulfates) with many metals. These are frequently very stable and, indeed, they are the most important mineral compounds of several of the more electropositive elements. They have been discussed in detail under the appropriate elements. Sulfates can be prepared by: dissolution of metals in aqueous H2S04 (e.g. Fe); neutralization of aqueous H2SO4 with metal oxides or hydroxides (e.g. MOH); acids decomposition Of Of (e.g. carbonates) with aqueous H2SO4;

Peroxosulfuric acids, H2S05and H2S208

Anhydrous peroxornonosulfuric acid (Caro's acid) can be prepared by reacting chlorosulfuric acid with anhydrous H202 HOOH + ClS02(0H) d HOOSOz(0H) + HCl
'93

K. NAKAMOTO,Infrared Spectra of Inorganic and Coordination Compounds, 2nd e&., Wiley, New York, 1970, 338 pp. (See also J. Am. Chem. SOC. 79. 4904-8 (1957) for detailed correlation table.)

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