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.
T O
sample. During this procedure, stopcock i is turned t o
permit the evaporating liquid air t o escape into t h e
atmosphere. Since t h e apparatus must be cleared with
fresh air and t h e determination is being made in the
gas t o be tested, stopcocks i and h are now turned t o
place t h e liquid air chamber in communication with f
and t h e tube thus filled with “pure air’’ for sweeping
the train.
The apparatus is contained in a cabinet 24 in. X 2 0 in.
X 7 in.
A determination should take about I j min. and
should be accurate t o from 0.003 t o 0.005 per cent
carbon monoxide (0.3 t o 0.5 part in 10,000).
SUMMARY
The iodine pentoxide method for determining low
concentrations of carbon monoxide has been investi-
gated with reference t o its use with dilute motor ex-
haust gas. The type of apparatus heretofore used was
found t o give appreciably high results owing t o the pres-
ence of small amounts of unburned gasoline. A new
iodine pentoxide apparatus (Type 11) has therefore
been developed. All of the interfering gases are first
removed a t t h e temperature of liquid air. This
method has been found quite satisfactory for deter-
mining carbon monoxide in small quantities in the
presence of gasoline vapor.
A portable iodine pentoxide apparatus has been de-
signed which should permit a determination t o be made
in I 5 min. with an accuracy of from 0.003 t o 0.00 j per
cent carbon monoxide (0.3 t o 0.5 part in 10,000).
ACKKO WLEDGMENT
Appreciation is expressed t o Dr. A. C. Fieldner, super-
vising chemist in charge of tunnel gases investigation,
and Dr. Yandell Henderson, in charge of physiological
investigations, for valuable suggestions and advice, and
t o Mr. W. B. Fulton for making many of the determina-
tions herein reported.
THE USE OF CATALYSTS IN T H E SULFONATION OF
AROMATIC COMPOUNDS
By Joseph A. Ambler and William J. Cotton
COLORLABORATORY,
U. S. BUR$AUOF CHEMISTRY, WASHINGTON, D. c.
Received May 12, 1920
During the course of experimentation on the vapor-
phase sulfonation of compounds, i t was found t h a t by
using the continuous method of Ambler and Gibbs,l
with a given set-up of apparatus and given tempera-
ture range, t h e amount of material sulfonated per
minute was practically constant; that is, the apparatus
had a certain “capacity” for sulfonation, since so
long as t h e baffies in the apparatus were not disturbed,
the free space for vapors and t h e absorbing or sulfonat-
ing surface were constant. The method, therefore,
provided a good means of studying the effect of various
substances introduced with the reacting materials,
and of ascertaining which were catalyzers of the
sulfonation reaction. This work is intended as intro-
ductory t o a much more complete study of sulfonation
catalysts. Inasmuch as t h e study will be unavoidably
1 U. S. Patents 1,292,950; 1,300,227; 1,300,228. A description of
this process will be published in subsequent papers.
12, NO.
delayed for some time, i t seems best t o publish t h e
work thus far accomplished, although it is incom-
plete.
Various workers have reported t h a t t h e sulfonation
of aromatic compounds m+y be accelerated by adding
different catalysts. T h e addition of sodium sulfate]
or various acid sodium sulfates2 has long been common
practice, and a similar use of potassium sulfate3 has
also been reported. It is also well known t h a t various
sulfonic acids can easily be further sulfonated in t h e
form of their sodium or potassium salts; whereas, if t h e
free acid is used, t h e introduction of more sulfonic acid
groups becomes extremely difficult, as, for example,
in t h e production of benzene-~,g, j-trisulfonic acid4
from t h e salts of benzene disulfonic acid. I n all of
these cases, t h e large amount of the alkali salts used
makes it almost impossible t o decide whether the action
is catalytic, or caused by t h e greatly increased boiling
point of t h e sulfuric acid-alkali sulfate mixture used.
Other substances recommended as accelerating
catalysts are vanadium6 in t h e sulfonation of anthra-
quinone, and iodine6 in t h e sulfonation of benzene.
Compounds of mercury, aluminium, iron, lead, arsenic,
bismuth, cadmium, and manganese7 have also been
studied from the standpoint of their effect upon the
position in the molecule taken by the entering sulfonic
acid group.
EXPERIMENTAL DETAILS
I n t h e present work some of t h e compounds men-
tioned above have been studied t o ascertain whether
they exert any accelerating (catalytic) effect on t h e
sulfonation of benzene, and all so far examined have
shown some catalytic action. These substances are
copper sulfate, mercuric sulfate, vanadium pentoxide,
sodium sulfate, chromic acid, potassium sulfate,
lithium sulfate, and mixtures of sodium sulfate an&
vanadium pentoxide. I n every case the substance was
dissolved in 7 0 per cent sulfuric acid, thus insuring
a constant concentration of the catalyst in the re-
action tower. The concentration of catalyst is ex-
pressed as the percentage of the characteristic element,
although in making t h e solutions t h e above-mentioned
compounds were actually added t o t h e sulfuric acid.
For example, 0.1 per cent copper means t h a t t h e
amount of copper sulfate used was chemically equiva-
lent t o t h a t weight of copper which was 0.1 per cent
of the weight of the sulfuric acid.
I n each case t h e experiment was carried on for from
a n hour t o an hour and a half, after which time t h e
products of t h e reaction were discarded, a t t h e same
time “cutting in” with weighed quantities of acid and
benzene. The experiment was considered as starting
1 Girard, Bull. soc. chim., 26 (1876), 333; Miihlhauser, Dinglev’s poly-
tech. 1,.263 (1887), 154.
2 Lambert, D. R. P. 113,784 (1899); Kendall, U. S. Patent 1,217,462
(191 7).
8 Jackson and Wing, Am. Chem. J., 9 (1887), 325.
4 Jackson and Wing, LOC. cit.; Behrend and Murtelsmann, Ann., 378
(1911), 352.
6 Thummber, D. R. P. 214,156 (1909).
5 Hinemann, Brit, Patent 12,260 (1915).
7 Iljinsky, Ber., 36 (1903), 4194; Schmidt, Ibid., 37 (1904), 66; Dunsch-
mann, Ibid., 37 (1904), 331; Holdermann, Ibid., 39 (1906), 1250; Dimrotb
and Schmaedel, Ibid., 40 (1907), 2411; Behrend and Mertelsmann, LOG.
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.