HIGHLIGHTS

Sulfuric Acid from Sulfur Trioxide and WaterA Surprisingly Complex Reaction**
Ralf Steudel"
Sulfuric acid is not only one of the longest known and utilized
chemicals but also one of the most important compounds of all;
the annual worldwide production varied in the last four years
between 135 and 152 million tons depending on the economic
situation."' Under these circumstances it is surprising that the
structure of the free H,SO, molecule was experimentally determined only in 1981: microwave spectroscopy of gaseous
H,S0,'21 showed that the molecule has C , symmetry; the two
hydrogen atoms are situated anli to one another (Fig. 1).Previ-

Fig. 1. Structure of the H,SO, molecule in

the vapor phase (bond lengths in pm). The
geometrical parameters were obtained by a b
initio MO calculations [4]: values in italics
from microwave spectroscopy [ 2 ] .

162.3

ously, a somewhat more symmetric conformation with the hydrogens in trans positions (symmetry C,,,) had been assumed
since the vibrational spectra of H,SO, vapor had been assigned
in this point group. In the meantime the C, conformation of
H,SO, has been confirmed as the most stable structure by various ab initio MO ~alculations.[~
- 6 1 These findings demonstrate
once more that the structure of highest symmetry is not always
the most stable one, as is often claimed.
Industrially, sulfuric acid is produced from sulfur trioxide and
water. However. the direct reaction of these reagents is not
practical for several reasons. First, reaction (a) is highly exotherSO,(g) + H,O(g)

H,SO,(g)

Afl; = - 92 kJmol-'

(a)

mic, which results in high temperatures and thereby leads to

problems with corrosion. Second, the very hygroscopic sulfuric
[*] Prof. Dr. R. Steudel
Institut fur Anorganische und Analytische Chemie der

[**I

Technischen 1Jniversitlit
D-10623 Berlin (Germany)
Telefiw: Int. code + (30)314 265 19
e-mail s t e u d e h wap0204.chem.t~-berlin.de
Sulfur Compounds. Part 189. The assistance of Dr. Yana Drozdova in the
preparation of Figures 1 --4 is gratefully acknowledged. Part 188: M. Pridohl,
R. Steudel, J. Buschmann. P. Luger, Z. Anorg. M g . Chem., in press.

Anyew. C'lrein.I n / E d Engl 1995. 34. N o . I 2

!I;

acid molecules formed would react with water vapor to give a

mist of H,SO;n H,O droplets which are difficult to precipitate.
Therefore, the gas prepared by the contact process and containing SO, as well as S,O, is washed with concentrated sulfuric
acid (98 O h ) resulting in polysulfuric acids ; these are then hydrolyzed by waterC7][Eqs. (b)-(e)].

+ HzSO, eH,S,O,
S,O, + HzSO,
H,S,O,,
HzO + H,S,O, e2HzS0,
SO,

Nevertheless, the simple reaction according to Equation (a) is

also of considerable interest, for example, in context with the
formation of sulfuric acid in the earth's atmosphere, where
H,SO, mainly results from SO,. To a large extent the latter is
of anthropogenic origin, resulting in the phenomenon of acid
rain in certain regions of the northern hemisphere. However, as
recent results show, the pathway from SO, to H,SO, is rather
complex, although very interesting. In the atmosphere SO, is
mainly oxidized by OH' radicals which are generated photochemically from electronically excited oxygen atoms and waterC8I [Eqs. (f)-(h)]. The resulting HOSO; radicals react rapidly
and exothermically with dioxygen to give SO,"] [Eq. (i)]
0,

hr.
-+

0 , + O('D)

O(lD) + H,O

20H'

--t

+ SOz ( + M)
HOSO; + 0,

OH'

------*

HOSO; ( + M)

-f

HO;

+ SO,

(1)

(M = collision partner). Since reaction (h) is slower than reaction (i), it is rate determining. The HO; radicals react with NO
to give NO, and OH' thus regenerating the latter.
Because of the low SO, partial pressure in the atmosphere the
equilibrium (b) is of no importance. It therefore may seem that
SO, and H,O can simply combine according to Equation (a) to
give H,SO,. However, this reaction occurs in several steps and
only under certain conditions. Initially, the Lewis acid SO, and
the Lewis base H,O react, analogously to other reactions of SO,
with bases, to give an adduct SO,.H,O [Eq. (j)]. This adduct

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HIGHLIGHTS
was first detected in matrix isolation experiments by vibrational
spectroscopy .[lo, 11] The spectra showed that the product has a
H,O-SO, bond rather than a hydrogen-bonded structure,
HOH . OSO,. A precise structural characterization was
achieved by high-level ab initio MO calculations (Fig. 2) . [ 3 - 5 1
The most accurate of these calculations showed the SO, group
slightly pyramidalized; the "intermolecular" S -0 bond length

dimer, the structure of which is well known [Eq. (k)]. There are
now two possibilities: either H,O can react with H,O.SO, or

(H,O), attacks SO, directly. In both cases this results in the

formation of the adduct (H,O),.SO,, the structure of which has
been determined by ab initio methods (Fig. 31eft).[51This structure indicates that a proton migration should be much easier
since the HOH . . . OSO, distance of 210.8 pm is considerably
smaller than in the case of H,O-SO, (> 250 pm). However, the
formation of H,SO, from (H,O),.SO, requires the synchronized migration of I W O protons in the corresponding hydrogen
bonds. The transition state structure (Fig. 3 right) is character-

Fig. 2. Left: Structure of the adduct H,O.SO, according to ab initio MO calculations (distances in pm). The two hydrogen atoms are almost eclipsed by two oxygen
atoms of SO, (overall symmetry C,), The intermolecular H . . ' 0 distance is larger
than the intermolecular S . . ' 0 distance. Therefore, the proton migration requires
a considerable activation energy 141. Right: Transition state of the reaction
H,O,SO, + H,SO, according to ah initio MO calculations [4].

between the two components is 254 ~ m . [Surprisingly,

~l
the hydrogen atoms have no close contacts to the oxygen atoms of the
SO, group but point slightly in the oposite direction; the angle
between the two molecular planes is 22.[41Very recently the
rotational spectrum of H,O.SO, was measured by FT microwave spectroscopy["' but only a few molecular parameters
could be determined. Assuming that do, and aHOH
have the same
values as in free H,O molecules, the "intermolecular" S - 0
bond length was determined as 243.2(3) pm. The SO, fragment
is in fact slightly pyramidal; the angle between the two molecular planes is 13". The torsional angle around the "intermolecular" S - 0 bond could not be
Previously it had been assumed that H,O.SO, can isomerize
to H,SO, by a simple proton migration; however, in 1985 it was
already demonstrated by MO calculations that this isomerization requires a rather large activation energy.l3]Very recent ab
initio MO calculations,[41 performed at the very high level
MP4SDQ/6-311+ G(2df,p)//RMP2(fu)/6-31+ G* (taking the
zero point energy calculated at level RMP2(fu)/6-31G* into
account) yielded an activation energy of 114 kJmol-' for the
reaction H,O.SO, -P H,SO, at 0 K. This energy has to be compared with the reaction enthalpy of reaction (j) which is only
- 33 kJ mol- '. Therefore, it has to be concluded that any activation of H,O.SO, would result in dissociation rather than
isomerization. In other words, the formation of H,S04 by
this route is impossible! If the thermal energy at 25 "C is taken
into account the free reaction enthalpy for reaction (j) is found
to be AG:y8 = 0 kJmol-' (because of the negative reaction entropy), from which the equilibrium constant K =
exp( - AG:,,/RT) = 1 is obtained. The free activation enthalpy AGZY8 of the isomerization H,O.SO, -+ H,SO, is
119.6 kJ mol- .L4]
This picture changes dramatically if a second water molecule
is added. In the vapor phase H,O is in equilibrium with its
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U
Fig. 3. Left: Structure of the adduct from SO, and (H20), according to ab initio
MO calculations (distances in pm) [ 5 ] . The intermolecular S . . ' 0 distance
(233.1 pm) is smaller than that in SO,.H,O (245.3 pm). Right: Transition state of
the isomerization (H,O),.SO, --t H,SO,.H,O. The two protons in the almost linear hydrogen bonds move synchroneously and clockwise towards their new bonding
partners [S].The structure may be interpreted as a cyclic ion pair, H,O+HSO:. The
final product H,O.H,SO, is not an ion pair.

ized by a six-membered ring; this lies about 96 kJmol-* higher

in energy than the adduct (H,O),.SO,, the formation of which
from 2H,O and SO, is exothermic by 110 kJmol-'. In other
words, in this case the activation energy is smaller than the
dissociation energy, and the isomerization H,O.SO, -+
(H,O).H,SO, may proceed without problems. The energy profiles of reactions (a) and (1) are shown in Figure 4.

H2S0,.

40

Fig. 4. Energy profiles for the reactions of SO, with H,O via H,O.SO, to H,SO,
and of SO, with (H,O), via (H,O),SO, to H,O.H,SO,. The Y axis is the reaction
coordinate: TS = transition state.

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34. No. 12

HIGHLIGHTS

Recent kinetic measurements[' 31 support the idea of a secondorder reaction with respect to H,O [Eq. (I)]. Such measurements
are all but trivial, since wall reactions have to be suppressed.
2H20

+ SO,

, H,SO,

+ H,O

(1)

Using a reactor with turbulent flow, designed to minimize wall

reactions, it could be demonstrated that SO, on mixing with
water vapor at 22 "C disappears in a reaction of order 2.04 with
respect to the H,O concentration. Reaction (I) proceeds in two
steps: dimerization of H,O according to Equation (k) and reaction of the dimer with SO, to give H,SO, and H,O. Because of
the slightly exothermic pre-equilibrium (k), the rate of reaction
(I) increases with decreasing temperature.[I3]The concentration
of (H,O), in the atmosphere has been estimated to be approximately l 0 l 4 cm-3 at ground level and approximately 104cm-3
at an altitude of 40 km. These concentrations are sufficient to
allow the formation of significant amounts of H,SO, by reaction (I)." 3' It should however be pointed out that about 50% of
the atmospheric SO, is oxidized as an aqueous solution, that is
dissolved in the droplets of clouds, rather than in a honiogeneous gas phase reaction. Suitable oxidants for the dissolved
SO, are ozone and hydrogen peroxide, but in addition peroxoacetic acid, methyl hydroperoxide, and peroxoacetylnitrate are
discussed. The relative importance of these reagents depends on
pH and temperature.[*]
Besides SO, tremendous amounts of carbonylsulfide (COS)
and dimethylsulfide (DMS) are released into the atmosphere.
DMS is of biological origin, produced mainly by marine phytoplankton, and together with its oxidation products and COS it
yields the "background" of sulfur compounds in the atmosphere. The oxidative degradation of DMS is complex but
among its products also yields SO, as in the case of COS.['41
Finally. it should be mentioned that the sulfuric acid formed
in the atmosphere causes a variety of effects. H,SO, molecules
attract water molecules and form droplets of less than 1 pm
diameter (the size depends on the humidity). These droplets
absorb atmospheric ammonia and form what is called a liquid
"sulfate aerosol". This aerosol not only reduces the visibility but
also increases the earth's albedo. As a consequence, the reflection of sunlight is enhanced and it is most probably this effect
that partly compensates the global warming resulting from the
greenhouse effect in industrialized areas." 5, ' 6 ] Approximately
90 '10 of the anthropogenic SO, emissions occur in the northern

Angcii,. Clirm. Inr.

Ed. ng/. 1995, 34. Nu. 12

0 VCH

hemisphere. The half-lifes of SO, and H,S04 in the atmosphere

are only a few days. Therefore, these compounds are not transported to the southern hemisphere, in contrast to CO,, COS.
CH,, N,O, and fluorochloro hydrocarbons. These facts possibly explain why most of the global warming has been observed
in the southern hemisphere although most of the air pollution is
generated in the northern herni~phere."~]
As acid rain, H,SO, causes well-known damage, but at the
same time serves as a nutrient for plants which depend on the
availability of sulfate ions for the synthesis of sulfur-containing
amino acids. There are good reasons to demand a rigorous
reduction of SO, emissions; however, this will result in an increased need for sulfur-containing fertilizers for sulfur-deficient
farm land.
German version: Angcw. Chem. 1995. 107. 1433-1435

Keywords: atmospheric chemistry hydrogen bonds structure

elucidation . sulfur compounds . sulfuric acid
Sulphur 1994. 235 (Statistical Suppl.. Table 4).
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K. Morokuma, C. Muguruma. J. Am. C/iem. Soc. 1994. 116, 10316.
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H. Muller. U . Sander, U . Rothe, R. Kola, Ullnzrinnr E n c i d . Ind. Chrm. 1994.
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1995. YY. 501
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R. J. Charlson. T. M. L. Wigley. Sci. Am. 1994, Nr. 2, 18.
Clouds reflect about 30% of the sun's radiation. Most recent results indicate
that clouds absorb more energy than previously assumed: R. D. Cess. M. H.
Zhang. P. Minnis. L. Corselti. E. G. Dutton. B. W. Forgan. D. P. Garber,
W. L. Gates, J. J. Hack, E. F. Harrison, X. ling. J. T. Kiehl. C. N . Long, J.-J.
Morcrette, G. L. Potter, V. Ramanathan. B. Subasilar. C H. Whitlock. D. t:
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499

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