CHAPTER 1

Introduction

Chlorosulfonic acid was first prepared by Williamson' in 1854 by the action of

phosphorus pentachloride on concentrated sulfuric acid and late? by the direct
action of hydrochloric acid on sulfur trioxide. Other methods of preparation
include: distillation of fuming sulfuric acid (oleum) with phosphorus pentoxide in
a stream of gaseous hydrogen chloride; the action of phosphorus trichloride or
oxychloride, chlorine, thionyl chloride, or sulfur monochloride on concentrated or
fuming sulfuric acid; passing a mixture of sulfur dioxide and chlorine into glacial
acetic acid; or reaction of carbon tetrachloride with fuming sulfuric acid.3
Chlorosulfonic acid is also named chlorosulhric acid in Chemical Abstracts,
but chlorosulfonic acid is the commercial name by which it is more widely
known. Other names are: sulfuric chlorohydrin, sulfuric acid chlorohydrin, mono-
chlorosulfuric acid, monochlorosulfonic acid, chlorohydrated sulfuric acid and
sulfuryl hydro~ychloride.~

1 Manufacture
Modern chemical plants manufacture chlorosulfonic acid by the direct union of
equimolar quantities of sulfur trioxide and dry hydrogen chloride gas.4 The
process is a continuous flow operation and, since it is highly exothermic, heat
removal is essential to maintain the reaction temperature at 50-80 "C. The sulfur
trioxide may be used in the form of 100% liquid or as a dilute gaseous mixture
from a contact sulfuric acid plant. Likewise, the hydrogen chloride may be 100%
gas or in a diluted form. The chemical reactor may be a packed column cooled by
a water-cooled condenser to moderate the vigour of the reaction and hence avoid
decomposition of the product. The chemical plant must be composed of non-
corroding materials such as glass, glass-lined steel, enamel or steel coated with
polytetraethylene (PTFE) so that the chlorosulfonic acid is not much contaminated
with iron. A typical analysis of commercial chlorosulfonic acid would be as
follows: C1SO3H 98-99.5%; H2S040.2-2%; free SO3 0-2%; HCl 0-0.5% and
Fe 5-50 ppm. Chlorosulfonic acid may be stored and transported in steel
containers, but in this case the iron content will be in the range 25-50 ppm. The
annual production of chlorosulfonic acid increased substantially after World War

1
2 Chapter 1

I1 due to expansion of the synthetic detergent industry and of dyes, drugs and
pesticides. Worldwide there are approximately twenty listed manufacturers of
chlorosulfonic acid: in the USA the two major ones are EI DuPont de Nemours
Co Inc (> 30 000 t yr-*) and the Gabriel Chemical Co (> 13 000 t yr-I). The price
of chlorosulfonic acid has risen from approximately US$ 209 t-' in 1977 to US$
389 t-' in 1991. Further details of the preparation of chlorosulfonic acid are given
in Chapter 10, p 272.

2 Physical Properties
Chlorosulfonic acid (C1SO3H) is a colourless or straw-coloured liquid which
fumes in air and decomposes slightly at its boiling point. The physical properties
are shown in Table 1;4 these vary slightly from sample to sample reflecting the
different amounts of the various impurities present, e.g. hydrogen chloride, sulfur
trioxide and related compounds. It is difficult to prepare a really pure sample of
chlorosulfonic acid because of its instability at the boiling point, even under
reduced pressure, which tends to degrade rather than purify the molecule. Pure
chlorosulfonic acid has been obtained by fractional crystallization. Chlorosulfonic
acid is a strong acid which is toxic and corrosive and behaves as a dehydrating,
oxidizing and chlorinating agent. It is soluble in halocarbons containing hydrogen;
for instance, chloroform, dichloromethane and 1,1,2,2-tetrachloroethanebut is
only sparingly soluble in carbon tetrachloride and carbon disulfide. It is soluble in
liquid sulfur dioxide, sulfuryl chloride, acetic acid, acetic anhydride, trifluoroace-
tic acid, trifluoroacetic anhydride and nitrobenzene.

Table 1 Physical properties of chlorosulfonic acid, ClS03H

Property klue
~~ _____

Mol. wt. 116.53 1

MP ("C) -81 to -80
Bp ("C) at 760 mmHg 151-152
Bp ("C) at 19 mm Hg 74-75
Specific gravity (density), dp(g rn1-I) 1.753
Viscosity, mPa.s (= cP) at 15.6 "C 3.0
Viscosity, mPa.s (= cP) at 49 "C 1.7
Refractive index, :n 1.437
Dielectric constant at 15 "C 6 0 f 10
Electrical conductivity (ohm.cm) at 25 "C 0.2-0.3 X
Vapour density at 2 16 "C (kg m-3)(a) 2.4
Heat of formation, AHf, 298, (kJ mol-I) -597.1
Specific heat, kT kg-' K-' 1.18
Heat of vapourization (J g-') 452-460
Heat of solution in water (Hrnol-') 168.6
(a)Vapourdensity is not precise because chlorosulfonic acid partially decomposes at the boiling point

The structure of chlorosulfonic acid 1 was proved by Dharmatti' who showed

by magnetic susceptibility measurements that the chlorine atom was directly
Introduction 3
attached to the sulfur atom and further supporting evidence was obtained from
Raman spectral ~ t u d i e s . ~ ? ~
0
If
CI-S-0-H
II
0
1

3 Chemical Properties
Chlorosulfonic acid is a powerful acid with a relatively weak sulfur-chlorine
bond. It fumes in moist air producing pungent clouds of hydrogen chloride and
sulfuric acid (Equation 1).

CIS03H + H20 H2S04 + HCI (1)

When chlorosulfonic acid is heated it partially decomposes into sulfuryl

chloride (S02C12), sulfuric acid, sulfur trioxide, pyrosulfuric acid (H2S207),
hydrogen chloride, pyrosulfuryl chloride (C12S205) and other compounds. At
170 "C, there is an equilibrium between chlorosulfonic acid, sulfuryl chloride and
sulfuric acid (Equation 2). Sulfur dioxide and chlorine are not observed when
chlorosulfonic acid is heated between 170 and 190 "C, but do appear at higher
temperatures or when it is heated in a sealed tube (Equation 3).3
170 "C
2CIS03H 4 * SO2CI2 + H2S04
>190 "C
2CIS03H .L CI2 + SO2 + H2SO4
When chlorosulfonic acid is treated with powerful dehydrating agents like
phosphorus pentoxide, it is converted into its anhydride, pyrosulfuryl chloride
(C12S205).Chlorosulfonic acid, by boiling in the presence of mercury salts or
other catalysts, decomposes quantitatively into sulfuryl chloride and sulfuric acid.
It functions as a chlorinating agent with sulfur, arsenic, antimony and tin and
yields sulfur dichloride and the tetrachlorides of the other element^.^ With
powdered tellurium or selenium, chlorosulfonic acid gives cherry-red or moss-
green colours respectively and these can be used in spot tests for the acid. On
heating with charcoal, it is decomposed with the evolution of sulfur dioxide,
hydrogen chloride and carbon dioxide. In synthetic organic chemistry, chlorosul-
fonic acid can be used for sulfation of alcohols (Equation 4); sulfamation of
amines (Equation 5); and the sulfonation and chlorosulfonation of aromatic
compounds (Equations 6 and 7). In the latter reaction, there must be an excess (at
least two equivalents) of the reagent present. All these reactions depend on the
relative weakness of the sulfur-chlorine bond in chlorosulfonic acid. Chlorosulfo-
nic acid only reacts slowly with saturated aliphatic hydrocarbons in the absence
of a double bond or other reactive site, such as a tertiary hydrogen atom. Straight
chain aliphatic alcohols, e.g. lauryl alcohol (dodecan- 1-01) can therefore be
sulfated by chlorosulfonic acid without degradation or discolouration which often
occurs with sulfur trioxide; this is important in the manufacture of hair shampoos,
4 Chapter 1

like sodium lauryl sulfate 2 (Equation 8); the sulfation reaction is often carried
out in pyridine solution.
ROH + CIS03H * ROS03H + HCI
pyridine
RNH2 + CIS03H * RNHS03H + [HCI]

ArH + CIS03H 4 ArS03H + HCI (6)

ArH + 2CIS03H ArS02CI + H2SO4 + HCI (7)

~C12H250H+ CIS03H -
pyridine
n-C12H250S03H+ [HCI]
NaOH (aq.)
* n-C12H25S04- Na' (8)
2

With primary or secondary amines, chlorosulfonic acid yields the correspond-

ing sulfamic acid (Equation 5); this reaction with cyclohexylamine afforded the
artificial sweetener sodium cyclamate 3 (Equation 9). In contrast to alkanes,
alkenes readily react with chlorosulfonic acid to give the alkyl chlorosulfonates;
thus ethylene (ethene) is absorbed by chlorosulfonic acid to give ethyl chlorosul-
fonate 4 (Equation 10).

Aromatic hydrocarbons also react smoothly with an equimolar amount of

chlorosulfonic acid or an excess of the reagent to yield either the sulfonic acid or
the sulfonyl chloride (Equations 6 and 7). The direct conversion of aromatic
compounds into their sulfonyl chlorides (chlorosulfonation or chlorosulfonylation)
is probably the most important reaction of chlorosulfonic acid because sulfonyl
chlorides are intermediates in the synthesis of a wide range of sulfonyl
derivatives. The process is of wide application because many substituents on the
aromatic ring, e.g. alkyl, alkoxy, amide, carboxy, cyano, hydroxy, nitro and
multiple bonds are unaffected by the reagent.
Chlorosulfonation is essentially an electrophilic substitution reaction, conse-
quently the reaction is facilitated by the presence of electron-donor groups, like
alkyl, alkoxy and hydroxy, when it proceeds under relatively mild conditions, e.g.
the minimum excess (approx. two equivalents) of the reagent, temperatures of
-5 "C to 25 "C and an inert diluent such as chloroform. On the other hand, when
electron-withdrawing groups, e.g. nitro, carbonyl or carboxy are present, the
reaction requires more drastic conditions, e.g. a large excess of the reagent (five
to ten equivalents) and heating to 100-150 oC.8
The use of chlorosulfonic acid for the synthesis of organic sulfonyl chlorides
has been reviewed. The work before 1943 is described with extensive references
Introduction 5
by Suter,' by Jackson3 and, specifically for aromatic hydrocarbons, by Suter and
Weston.lo
More recent reviews of sulfonation were carried out by Gilbert,' Cerfontain,I2
Andersen13 and Taylor14 and of chlorosulfonation by Bassin, Cremlyn and
Swinbourne.l5
The use of chlorosulfonic acid for preparation of several important arylsulfonyl
chlorides has been de~cribed.'~.'~ However, depending on the nature of the
substrate and the experimental conditions, reaction with chlorosulfonic acid may
also yield diary1 sulfonesi8 or chlorinated products."
Chlorosulfonic acid is widely used in organic qualitative analysis to prepare
solid derivatives from liquid or low melting aromatic compounds, e.g. hydro-
carbons, halides and ethers.'6y20The procedure involves conversion of the aromatic
compound into the sulfonyl chloride, which is subsequently reacted with ammonia
to yield the solid sulfonamide derivative which is suitable for melting point
determination. Chlorosulfonic acid reacts with carboxylic acid anhydrides to give
excellent yields of the acid chlorides2' (Equation 11).
0

4 Safety
Chlorosulfonic acid reacts explosively with water producing fumes of hydrogen
chloride and sulfuric acid; the pungent vapour is toxic and highly irritating to
eyes, mucous membranes, skin and the respiratory tract.22
When using the reagent, protective clothing, gloves and safety goggles are
needed, because chlorosulfonic acid is highly corrosive and causes severe burns in
contact with skin. Experiments using chlorosulfonic acid must be performed in an
efficient fume cupboard. The acid is not itself flammable, but it can cause fires by
contact with combustible materials because of the heat of r e a ~ t i o n . ~Spills.~~
should be carefully diluted with large volumes of water. Absorption onto
materials, such as expanded clay, diatomaceous earth, sand or soda ash mixture is
effective, especially the latter since soda ash also partially neutralizes the acid.

5 Uses
Chlorosulfonic acid is employed in the manufacture of synthetic detergents such
as sulfates of alkenes or unsaturated oils, polyoxypropylene glycol, long chain
alcohols, alkylarenes or alkyl diphenyl ether^.^ It is also extensively used in the
manufacture of sulfonamide antibacterials (sulfa drugs), diuretics and other
pharmaceuticals, pesticides, artificial sweeteners (saccharin), disinfectants (chlor-
amine and dichloramine T), plasticizers, dyes and pigments, sulfonyl polymers as
plastics, and ion exchange resins. Chlorosulfonic acid is an oxidizing and
6 Chapter 1

dehydrating agent and functions as a catalyst in the esterification of aliphatic

alcohols, alkylation of alkenes, and synthesis of alkyl halides from alkenic halides
and isoalkanes containing tertiary hydrogen. It is used as a vulcanization
accelerator, a source of anhydrous hydrogen chloride and in the tanning, textile
and paper industries.
Overall, the approximate breakdown of the commercial applications of chloro-
sulfonic acid is as follows: detergents 40%; pharmaceuticals 20%; dyes 15%;
pesticides 10% and miscellaneous uses, e.g. plasticizers, ion-exchange resins, etc.
15%.

6 References
1 A.W. Williamson, Proc. R. SOC.London, 1854, 7, 11.
2 A.W. Williamson, J: Chem. SOC.,1857, 10, 97.
3 K.E. Jackson, Chem. Rev., 1939, 25, 83.
4 C.E. McDonald, ‘Chlorosulfuric Acid’ in Kirk-Other, Encyclopaedia of Chemical
Technology,4th Edn, Vol. 6, Wiley, New York, 1993, 168.
5 S.S. Dharmatti, Proc. Indian Acad. Sci. Sect. A , 1941, 13, 359.
6 R.J. Gillespie and E.A. Robinson, Can. J: Chem., 1962,40, 644.
7 H. Gerding, J Chem. Phys., 1948, 46, 188.
8 R.B. Wagner and H.D. Zook, Synthetic Organic Chemistry, Wiley, New York, 1965,
822.
9 C.M. Suter, The Organic Chemistry of Sulfur, Wiley, New York, 1944. Reprinted
edition by Intra-Science Research Foundation, Santa Monica, California, 1969.
10 C.M. Suter and A.W. Weston, Org. React. 0, 1946, 3, 141.
11 E.E. Gilbert, Sulfonation and Related Reactions, Wiley, New York, 1965.
12 H. Cerfontain, Mechanistic Aspects in Aromatic Sulfonation and Desulfonation,
Interscience, New York, 1968.
13 K.K. Andersen, ‘Sulfonic Acid and Derivatives’ in Comprehensive Organic Chemistry,
D.H.R. Barton and W. Ollis (eds), Vol. 3, Pergamon Press, Oxford, 1979, 331.
14 R. Taylor, Electrophilic Aromatic Substitution, Wiley, Chichester, 1990, 337.
15 J.P. Bassin, R.J. Cremlyn and F.J. Swinbourne, Phosphorus, Sulfur and Silicon, 1991,
56, 245.
16 B.S. Furniss, A.J. Hannaford, V Rogers, P.W.G. Smith and A.R. Tatchell (eds), Vogelj.
Textbook of Practical Organic Chemistry, 5th Edn, Longman, Harlow, 1989, 877, 883,
1234, 1238.
17 R.J. Cremlyn, An Introduction to Organosulfur Chemistry, Wiley, Chichester, 1996,
100, 103, 219.
18 A. Rieche and W. Fischer, Angew. Chem., 1957, 69,482.
19 R.J. Cremlyn and T.N. Cronje, Phosphorus and Sulfur, 1979, 6, 459.
20 H.T. Openshaw, Laboratory Manual of Qualitative Organic Analysis, Cambridge
University Press, Cambridge, 1968, 27.
21 L.F. Fieser and M. Fieser, Reagents for Organic Synthesis, Wiley, New York, 1967,
139.
22 S.G. Luxon (ed), Hazards in the Chemical Laboratory, Royal Society of Chemistry,
Cambridge, 1992, 302.