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968 T H E J O U R N A L O F I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 1701. 12, NO.

T O

sample. During this procedure, stopcock i is turned t o delayed for some time, i t seems best t o publish t h e
permit the evaporating liquid air t o escape into t h e work thus far accomplished, although it is incom-
atmosphere. Since t h e apparatus must be cleared with plete.
fresh air and t h e determination is being made in the Various workers have reported t h a t t h e sulfonation
gas t o be tested, stopcocks i and h are now turned t o of aromatic compounds m+y be accelerated by adding
place t h e liquid air chamber in communication with f different catalysts. T h e addition of sodium sulfate]
and t h e tube thus filled with “pure air’’ for sweeping or various acid sodium sulfates2 has long been common
the train. practice, and a similar use of potassium sulfate3 has
The apparatus is contained in a cabinet 24 in. X 2 0 in. also been reported. It is also well known t h a t various
X 7 in. sulfonic acids can easily be further sulfonated in t h e
A determination should take about I j min. and form of their sodium or potassium salts; whereas, if t h e
should be accurate t o from 0.003 t o 0.005 per cent free acid is used, t h e introduction of more sulfonic acid
carbon monoxide (0.3 t o 0.5 part in 10,000). groups becomes extremely difficult, as, for example,
SUMMARY in t h e production of benzene-~,g, j-trisulfonic acid4
The iodine pentoxide method for determining low from t h e salts of benzene disulfonic acid. I n all of
concentrations of carbon monoxide has been investi- these cases, t h e large amount of the alkali salts used
gated with reference t o its use with dilute motor ex- makes it almost impossible t o decide whether the action
haust gas. The type of apparatus heretofore used was is catalytic, or caused by t h e greatly increased boiling
found t o give appreciably high results owing t o the pres- point of t h e sulfuric acid-alkali sulfate mixture used.
ence of small amounts of unburned gasoline. A new Other substances recommended as accelerating
iodine pentoxide apparatus (Type 11) has therefore catalysts are vanadium6 in t h e sulfonation of anthra-
been developed. All of the interfering gases are first quinone, and iodine6 in t h e sulfonation of benzene.
removed a t t h e temperature of liquid air. This Compounds of mercury, aluminium, iron, lead, arsenic,
method has been found quite satisfactory for deter- bismuth, cadmium, and manganese7 have also been
mining carbon monoxide in small quantities in the studied from the standpoint of their effect upon the
presence of gasoline vapor. position in the molecule taken by the entering sulfonic
A portable iodine pentoxide apparatus has been de- acid group.
signed which should permit a determination t o be made EXPERIMENTAL DETAILS

in I 5 min. with an accuracy of from 0.003 t o 0.00 j per I n t h e present work some of t h e compounds men-
cent carbon monoxide (0.3 t o 0.5 part in 10,000). tioned above have been studied t o ascertain whether
ACKKO WLEDGMENT they exert any accelerating (catalytic) effect on t h e
sulfonation of benzene, and all so far examined have
Appreciation is expressed t o Dr. A. C. Fieldner, super-
shown some catalytic action. These substances are
vising chemist in charge of tunnel gases investigation,
copper sulfate, mercuric sulfate, vanadium pentoxide,
and Dr. Yandell Henderson, in charge of physiological
sodium sulfate, chromic acid, potassium sulfate,
investigations, for valuable suggestions and advice, and
lithium sulfate, and mixtures of sodium sulfate an&
t o Mr. W. B. Fulton for making many of the determina-
vanadium pentoxide. I n every case the substance was
tions herein reported.
dissolved in 7 0 per cent sulfuric acid, thus insuring
a constant concentration of the catalyst in the re-
THE USE OF CATALYSTS IN T H E SULFONATION OF action tower. The concentration of catalyst is ex-
AROMATIC COMPOUNDS pressed as the percentage of the characteristic element,
By Joseph A. Ambler and William J. Cotton although in making t h e solutions t h e above-mentioned
COLORLABORATORY,
U. S. BUR$AUOF CHEMISTRY, WASHINGTON, D. c. compounds were actually added t o t h e sulfuric acid.
Received May 12, 1920 For example, 0.1 per cent copper means t h a t t h e
During the course of experimentation on the vapor- amount of copper sulfate used was chemically equiva-
phase sulfonation of compounds, i t was found t h a t by lent t o t h a t weight of copper which was 0.1 per cent
using the continuous method of Ambler and Gibbs,l of the weight of the sulfuric acid.
with a given set-up of apparatus and given tempera- I n each case t h e experiment was carried on for from
ture range, t h e amount of material sulfonated per a n hour t o an hour and a half, after which time t h e
minute was practically constant; that is, the apparatus products of t h e reaction were discarded, a t t h e same
had a certain “capacity” for sulfonation, since so time “cutting in” with weighed quantities of acid and
long as t h e baffies in the apparatus were not disturbed, benzene. The experiment was considered as starting
the free space for vapors and t h e absorbing or sulfonat- 1 Girard, Bull. soc. chim., 26 (1876), 333; Miihlhauser, Dinglev’s poly-
ing surface were constant. The method, therefore, tech. 1,.263 (1887), 154.
2 Lambert, D. R. P. 113,784 (1899); Kendall, U. S. Patent 1,217,462
provided a good means of studying the effect of various (191 7).
substances introduced with the reacting materials, 8 Jackson and Wing, Am. Chem. J., 9 (1887), 325.

and of ascertaining which were catalyzers of the 4 Jackson and Wing, LOC. cit.; Behrend and Murtelsmann, Ann., 378
(1911), 352.
sulfonation reaction. This work is intended as intro- 6 Thummber, D. R. P. 214,156 (1909).

ductory t o a much more complete study of sulfonation 5 Hinemann, Brit, Patent 12,260 (1915).
7 Iljinsky, Ber., 36 (1903), 4194; Schmidt, Ibid., 37 (1904), 66; Dunsch-
catalysts. Inasmuch as t h e study will be unavoidably
mann, Ibid., 37 (1904), 331; Holdermann, Ibid., 39 (1906), 1250; Dimrotb
1 U. S. Patents 1,292,950; 1,300,227; 1,300,228. A description of and Schmaedel, Ibid., 40 (1907), 2411; Behrend and Mertelsmann, LOG.
this process will be published in subsequent papers. c i t . ; Mohrmann, Ann., 410 (1915), 373.
Oct., I920 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 969

from this point in order t o be sure t h a t the reaction It should be noted here t h a t two experiments given
had become thoroughly established and t h a t every- in Table I do not appear in the second, viz., Na(1) and
thing about the apparatus was in a state of equilibrium K. Through a n unfortunate oversight the amount of
which could be maintained until the end of the experi- benzene disulfonic acid was not correctly determined,
ment; and t o obviate the large error inherent in the because no determination of the amount of catalyst
apparatus, due t o the fact t h a t i t took some time for contained in the barium salt was made.
the benzene vapors t o displace all the air in the ap- The experiment with no catalyst is typical of many
paratus, and for the sulfuric acid t o wet all the surfaces in which the amount of benzene sulfonated per minute
of the baffles and the walls of the tower, during which was always approximately 0.5 g. This figure repre-
time the apparatus did not operate a t its maximum sents the normal capacity of the apparatus.
capacity. DISCUSSION O F R E S U L T S
TABLEI
Wt. W t Benzene A study of Table I shows t h a t all the substances
Con c en - Mean Duration Sulfonic Sulfonated
tration Temp. of Expt. Acids per Min. used increased the amount of benzene sulfonated per
Catalyst Per cent ’C. Min. Grams Grams
minute, a n d t h a t these catalysts are divided into two
... ... 243 580 734 0.63
c u . . . . . . . . . . 0.1 25 1 185 301 0.80 general groups, viz., those which have a slight catalytic
Hg.. . . . . . . . . 0.1 243 232 386 0.82
v . . . . . . . . . . . 0.1 249 249 356 0.71 action, copper, mercury, vanadium, chromium, potas-
Na(1) . . . . . . . 0 . 1 252 291 649 1.10
Cr.. . . . . . . . . . 0.1 249 202 278 0.67 sium, lithium, and two of the experiments with sodium;
K . . . . . . . . . . . 0.17 257 292 479 0.82
and those which have a marked catalytic action, the
L i . . . . . . . . . . . 0.094 246 283 405 0.61
Na(I1) . . . . . . 0 . 5 255 300 492 0.83 first experiment with sodium, and the two experiments
Nn(II1) ...... 0 . 1 259 355 601 0.84
N a . ,. , , , , , . , 0.1
.
V . .’.. , , . , , , 0.05
V . , . . . . . . . . . 0.223
1 242 274
232
626
592
1.13
1.26
using both sodium and vanadium. The more marked
effect in the first experiment with sodium was caused
Na. . . . . . . . . 0.025} 249
by a small amount of vanadium, which had been used
Tables I and I1 give the critical data so far as the in the experiment just preceding i t , and which had not
catalysts are concerned. The “weight of sulfonic been completely removed from the tower.
acids” in Table I was found as follows: Total acidity, The most active catalyzer is obviously a mixture of
expressed in terms of sulfuric acid, was determined by sodium and vanadium in any reasonable proportion.
titration with standard alkali, using phenolphthalein The results also clearly show t h a t the sodium and
or thymolsulfophthalein for indicator. Actual sul- potassium sulfates in sulfonation mixtures have a
furic acid was determined with barium chloride as distinct catalytic effect, and t h a t the advantages
usual. The difference of these two determinations gained by their use are not entirely due t o the increased
represented sulfuric acid equivalent t o the sulfonic boiling point of the sulfuric acid.
acid present. The latter was temporarily assumed Another interesting fact brought out is the effect of
t o be benzene monosulfonic acid, and its amount the catalyst on the amount of disulfonic acid formed
calculated according t o the ratio : zHSO3.CeH6. per minute. This subject is t o be investigated further.
From this value i t was a simple matter t o calculate the Apparently the members of the first group of t h e
amount of benzene sulfonated per minute. periodic system, represented here by sodium and
TABLE
I1 lithium, accelerate the formation of disulfonic acid
in this type of sulfonation, while the mixture of
vanadium pentoxide d i t h sodium sulfate is still more
effective. The other catalysts apparently inhibit t h e
formation of disulfonic acid.

PHTHALIC ANHYDRIDE. IV-THE VAPOR PRESSURE


O F PHTHALIC ANHYDRIDE
.. ... 243 580 705 147 0.56 0.25
cu ........... 0.1 251 185 294 28 0.76 0.15 By K. P. Monroe
Hg ........... 0.1 243 232 377 36 0.78 0.16
v ............ 0.1 249 249 355 6 0.66 0.03 COLORLABORATORY,
U. S. BUREAUon CHEMISTRY, D. C.
WASHINGTON,
Cr ............ 0.1 249 202 274 13 0.66 0.06 Rec:ived June 1, 1920
Li ............ 0.094 246 283 380 95 0.61 0.34
Na(I1) ....... 0.5 255 300 463 111 0.70 0.37 The investigation of the vapor-pressure curve of
Na(II1) ....... 0.1 259 356 574 101 0.75 0.29
Na. . . . . . . . . . . phthalic anhydride was initiated t o assist in the solu-
v............ 242 274 595 121 1.00 0.44
v............ 0 223
249 232 569 88 1.15 0.39 tion of certain problems arising in the air-oxidation
Na. .......... 0:025
process recently developed by Gibbsl and his co-
These figures, however, were subject t o error, inas- workers. Although the results were obtained in a
much as some benzene disulfonic acid was always preliminary series of measurements, and are not of
formed. Table I1 contains corrected values, based the order of accuracy which i t was hoped t o obtain by
on the following calculation: The amount of di- repetition with a more refined mercury gage, they are
sulfonic acid was determined by analysis of the barium presented, since i t appears unlikely t h a t the author
salt of the sulfonic acids, making necessary corrections will resume the investigation.
for the catalyst itself when i t was found in the barium Phthalic anhydride, purified by a method previously
salt. The weight of sulfonic acids was then corrected described,2 was placed in a static isoteniscope of the
and, by using the t’wo ratios C&s : CsHsS03H and 1 See the previous articles of this series: “Phthalic Anhydride,” I,
by H. D Gibbs, THIS JOURNAL, 11 (1919), 1031, “Phthalic Anhydride,”
CsH,; : C&(S03H)2, the amount of benzene actually I1 and 111, by K P Monroe, I b i d . , 11 (1919). 1116 and 1119
sulfonated per minute was calculated. 1 Part 11, LOC.cit.