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Arthur Slator and The Chlorination of Benzene: Bull. Hist. Chem., VOLUME 28, Number 2 (2003) 95
Arthur Slator and The Chlorination of Benzene: Bull. Hist. Chem., VOLUME 28, Number 2 (2003) 95
actual supervisor of the task that Slator was about to known concentrations of iodine to the chlorine-benzene
begin. Both in Slator’s doctoral dissertation (1903) and solution generated iodine monochloride (ICl). He
the resulting publication (2), Luther received acknowl- showed that ICl did not attack benzene but remained
edgment as mentor. unchanged in the solution while catalyzing the chlorine-
benzene reaction. In his studies with this catalyst, Slator
Slator repeatedly distilled commercial, thiophene-
was thus able to measure amounts of remaining chlo-
free benzene until the boiling point was constant to
rine by deducting the titer attributable to ICl from the
within a few tenths of a degree. Chlorine, prepared from
total thiosulfate titer. He noted that, with this catalyst,
HCl and K2Cr2O7, was dried over H2SO4 and either
both chlorobenzene and benzene hexachloride were pro-
immediately dissolved in benzene or stored for later dis-
duced. However, his first concern was to determine the
solution. Dilution of the stock solution with benzene
rate of the consumption of chlorine, on the assumption
was used to prepare solutions for measurement of the
that the data would fit the first-order
velocities of reaction. With benzene
equation:
present in large excess, its concentra-
tion could be regarded as remaining es-
sentially constant. 1 [Cl]0
K = log (3)
Slator performed some reactions in t [Cl]t
sealed tubes, but when possible used the In this equation, Slator used K to
more convenient apparatus shown in indicate the rate constant, [Cl]o the
Fig. 2. The capacity of the reaction ves- initial concentration of chlorine and
sel, A, was not stated; but, because the [Cl]t the concentration after the elapse
performance of an experiment involved of t minutes. Slator found that K,
a succession of samplings, it was prob- which decreased as the ICl concentra-
ably not less than about 100 mL. The tion was decreased, was inversely pro-
vessel, which was immersed in a ther- portional to the square of this concen-
mostat set at 25o C, had an attached 3- tration. Additional experiments at 15o
mL pipet as shown. Measured samples C indicated a temperature coefficient
of the solution could then be withdrawn Figure 2. Apparatus for catalytic
of about 1.07 for a 10o C rise.
for analysis. An unspecified red sub- studies.
stance was used to color the bath liq- Slator investigated the distribu-
uid. According to Slator, the aim was to eliminate light tion of chlorine between the two products at tempera-
tures of 20 o, 25o and 80o C. Although he could not iso-
(presumably of the spectral region that could bring about
the chlorine-benzene addition) and thus to make the late the benzene hexachloride, he was able to determine
measurements in the dark. it indirectly. An ICl-catalyzed chlorine-excess benzene
reaction was run to completion, and the HCl thus formed
After the introduction of a measured amount of was titrated with Ba(OH)2 solution. This provided a
catalyst, the stirred mixture was sampled at specified measure of the total chlorine that had reacted. The ben-
times. Each sample was shaken with KI solution, and zene solution was then separated, washed with water,
the liberated I2 was titrated with Na2S2O3 solution, a and dried over CaCl2. A measured aliquot was heated
technique known since the 1850s (3). This provided a with alcoholic NaOH (presumably standardized by acid
measure of the remaining chlorine. To study the forma- titrimetry and in known amount) for 30 min. This treat-
tion of HCl, the titration was continued with Ba(OH)2 ment affects only the benzene hexachloride. From the
solution at 0o C. At this temperature hydrolysis of the decrease in titer, the amount of the hexachloride can be
S4O62- formed in the first titration is slow and does not calculated. Then the corresponding amount of chlo-
interfere. robenzene can be obtained by difference. Slator found
According to Slator, the use of iodine as a haloge- that the reaction temperature had almost no effect and
nation catalyst had been known since 1862. However, that an average of 72.5% of the chlorine is converted
applications of this catalyst in organic syntheses had been into chlorobenzene.
rare, because of possible attack on the reaction products Because carbon tetrachloride is not attacked by
or on other substances present. This restriction did not chlorine, Slator chose it as a solvent to examine the ki-
apply to Slator’s work, because the addition of small netic aspects of benzene itself. Numerous experiments
Bull. Hist. Chem., VOLUME 28, Number 2 (2003) 97
J. Chem. Soc., 1904, 85, 1286-1304; 1905, 87, 481-494; 12. W. A. La Lande, G. Molyneaux, and M. E. Aeugle, “Ben-
(with D.F. Twiss), 1909, 95, 93-103. zene Hexachloride,” U.S. Patent 2,696,509, Dec., 1954;
10. A. Slator, “Studies in Fermentation. I. The Chemical Chem. Abstr., 1955, 49, 4931e.
Dynamics of Alcoholic Fermentation by Yeast,” J. Chem. 13. N. N. Lebedev and I. I. Baltadzhi, “Kinetics and Reac-
Soc., 1906, 89, 128-142. tivity during Halogenation of Aromatic Compounds in
11. R. Luther and E. Goldberg, “Die Sauerstoffhemmung the Presence of Metallic Halides. I. Chlorination with
der photochemischen Chlorreaktionen in ihrer Beziehung Ferric Chloride as the Catalyst,” Kinetika i Kataliz, 1961,
zur photochemischen Induktion, Reduktion und 2, 197-204; Chem. Abstr., 1961, 55, 21757.
Activierung,“ Z. Phys. Chem., 1906, 56, 43-56. 14. H. P. Smith, W. A. Noyes, and E. J. Hart, “Photochemi-
cal Studies. XVI. A Further Study of the Chlorination of
Benzene, J. Am. Chem. Soc., 1933, 55, 4444-4459.
Gesellschft Deutscher Chemiker extends an invitation for applications for the Paul
Bunge Prize 2004, administered by the GDC and the Deutsche Bunsen-Gesellschaft
für Physikalishe Chemie. It consists of 7,400 Euro and honors outstanding publica-
tions in German, English, or French in all fields of the history of scientific instruments.
The application should also include a curriculum vitae and—if available—a list of
publications of the applicant. Deadline is September 30, 2003. Send nominations to:
Gesellschaft Deutscher Chemiker, Jutta Bröll, PO Box 90 04 40, D-60444 Franfurt/
Main, GERMANY; j.broell@gdch.de.