March, 1960 COMMUNICATIONS

TO THE EDITOR 38 1
TABLEI The approximate constancy of QI if the medium
VALUESOF Q1 = [CcBr+~]/[Cr+*][Br-]
AS A FUNCTION
OF is changed by the substitution of bromide ion for
AT I = 2.00 M
TEVPERATURE perchlorate ion a t constant ionic strength is taken
S o h . cotiign. 0 to indicate that: (a) the activity coefficient quo-
IBr -I 0.509 0.875 1.324 tient 7+3Y--1/7+2, with the subscripts indicating the
[Cr+8] + [CrBr+*] ,126 .lo5 0.106 ionic charges, is constant with this medium change:
[H+I .512 .473 .512 (b) outer-sphere association of Cr(OH2)6+3and Br-
W+I .737 .900 .857 does not occur to an appreciable extent, and (c)
Temp., "C. Values of QI X lOSb0
as stated above, an inappreciable amount of CrBrt+
0.0 0.97 0.93 0.98 is formed. It must be admitted that the observed
25.0 2.26 2.25 2.23 results could also be the consequence of a mutual
34.7 2.85 2.85 2.86 cancellation of these several factors.
45.2 3.63 3.83 3.74 The temperature coefficient of Q1 yields the
a A formula in brarkets reprcscnts the molnrity of the values, AH1 = 5.1 kcal. and A& = 4.9 e.u. The
specics. In each solution, perchlorate ion was prcxsent at, the approximately 100-fold lower stability of CrBr +2
concentration required for electroneutrality. Each tabu- (wit,h respect to and Br-) relative to the
lated value of QIis the average of two to four independent analogous stability of CrC1+2 is largely a conse-
measurements. The average difference of the independent
quence of the less positive value of A&. (For the
measurements from the average values waa 1.5%. The
values of Q1 X IO3 calculated for these temperatures using
AHI = +5. L kcal. and A SI= 4.9 e.u. are 0.98, 2.09, 2.79
reaction Cr+3 +
C1- = CrC1+2in 3.7 2cI HC104,
AH = 6.1 kcal. and AS = 17.2 e.u.6)
and 3.67, respectively.
( 4 ) For convenience, water molecule8 will not always be shown
strates the correctness of the assumption. A sum- in the first coordination shell of chromium(II1).
mary of the results is given in Table I. ( 6 ) H . S. Gates and E. L. King, J . Am. Chsm. Soc., 80, 601 1 (1968).

COMMUNICATIONS TO THE EDITOR

CATALYTIC OXIDATION OF HYDROGEN was refluxing slowly. Mass spectrometry gave
SULFIIIE TO SULFUR OVER A the effluent gas composition as 98.1 mole yonitrogen
CltYSTALlLINE ALUMINOSILICATE and 1.2 mole yo argon. The reaction was con-
tinued for 110 hours to yield a total of 2100 g. of
sir: sulfur. Several times during this period the
We have discovered that a synthetic crystalline reaction was stopped, the reactor cooled to room
aluminosilicate, known commercially as 13X temperature and reaction started again by the
molecular sieve,' is a particularly active cata- introduction of more of the gas mixture. When
lyst for the oxidation of hydrogen sulfide with the reaction was interrupted, the intense bluc
air. When gaseous sulfide was passed over the coloration of the catalyst disappeared. Occasion-
powdered zeolite in open air a t room temperature, ally small portions of the used catalyst had a per-
free sulfur was deposited on the catalyst surface manent light blue color. X-ray diffraction of the
initially, and the immediate evolution of heat was used catalyst indicated retention of a major part of
observed. Within seconds the catalyst became the crystallinity. No measurable loss of catalyst
incandescent and the gas stream ignited. activity was noted throughout the experiment.
Further studies were made using a tubular glass A gaseous mixture of 30 mole % hydrogen
reactor which was fitted with a coarse-porosity sulfide, 26 mole yo methane, 9 mole yo oxygen and
sintered disc for holding approximately 1 g. of 35 mole yonitrogen underwent a preferential oxida-
catalyst powder. A glass jacket surrounded the tion of the hydrogen sulfide when passed over the
reaction zone and contained 1-methylnaphthalene, catalyst. Clean, odorless sulfur was produced.
b.p. 245O, which served as a coolant. Hydrogen Analysis of the effluent gas by mass spectrometry
sulfide and air were introduced to the reactor a t indicated no loss or oxidation of methane while
flow rates of 360 and 960 ml. per minute, respec- from 95 to lOOyoof the oxygen was consumed.
tively, correspoinding to stoichiometric ratios of The oxidation of hydrogen sulfide to sulfur has
hydrogen sulfide and oxygen for sulfur formation. been catalyzed previously by bauxite, by soda-
On admitting the gases at room temperature the lime4 and by nickel and cobalt sulfides supported
catalyst turned .yellowish-brown in color, changing on alumina.6 Bauxite, the most widely used of
to a cobalt-blue color which persisted. During these catalysts, cannot initiate reaction at room
this color transformation sulfur started condensing temperature as does the aluminosilicate catalyst,
below the disc; within five minutes the coolant nor does bauxite effect the high conversions ob-
(1) Obtained froin ihe Lmde Company ace n W Brvck, W. G.
served in our studies.
EIersole and €1. M. Milton, J . A m Chem. Soc.. 7 8 , ZdJ8 (1956) (3) For examylc, see H. Grekel. Oil Gas J.. 6 T , NO.80,88 (19b9).
(2) R. M. Barrer, 1;. W. Bultitude and J. W. Suthorland, Trans. ( 4 ) H. N . Dunning. U. S. Patent 2,700,848(1956).
Faraday Soc., 5s. 1111 (19573. (5) J. Lefebvre. Bull. aoc. cham. France. 564 (1959).
382 COMMUNICATIONS
TO THE EDITOR VOl. 64

Since the crystalline aluminosilicate is a one- of the A zeolite, known as “molecular sieves,”5
component catalyst, as distinguished from multi- having “port” sizes of 4 to 5 A. Such observations,
component or amorphous catalysts, an opportunity in addition to providing an unusual type of cat-
is afforded for detailed study of the compositional alytic selectivity, support the concept of “intra-
and structural factors which impart catalytic crystalline catalysis,” in contrast to activity of the
activity for this reaction. exterior surface of crystals.
SOCONY MOBILOIL COMPANY With the Ca++ form of the A crystal, we have
RESEARCH DEPARTMENT GEORGET. KERR carried out the selective dehydration of 1-butanol
PAULSBORO, NEWJERSEY GEORGEC. JOHNSON in the presence of isobutyl alcohol. Conventional
~LECEIVED FEBRUARY 25, 1960 silica-alumina catalyst dehydrates both alcohols
at comparable rates. In contrast to the Ca++ form
INTRACRYSTALLINE AND MOLECULAR- of the “X” crystal, we observed cracking of only
n-paraffins over this solid t o only straight chain
SHAPE-SELECTIVE CATALYSIS BY ZEOLITE products, consistent with molecular sieve action
SALTS which does not allow egress of isomeric products.
sir: As an example of imparted activity, molecular-
shape-selective hydrogenation catalysts have been
We have foulid unexpected intrinsic catalytic prepared by incorporation of platinum in the A
activities on synthetic crystalline inorganic zeolite crystal. We have selectively hydrogenated 1-
salts. 1 . 2 butene in a mixture of 1-butene and 2-Me-propene.
The sodium aluminosilicate isostructural with In a mixture of equal volumes of 1-butene, iso-
faujasite, known as “13X,”3 is more active for the butene and hydrogen, at 25O with a contact tune
cracking of normal paraffins than conventional of ca. 0.1 sec., 50yoof only the 1-butene was con-
silica-alumina, cracking catalysts (10% ~ 1 1 2 0 3 , verted to butane. A platinum on alumina catalyst
g2O m.*,/g. :iudace area). If one replaces most of converted approximately equal quantities of both
the Na+ by (la++, the cracking activity is further olefins.
increased (Table I). The products from the Cat+
form resemble those from silica-alumina. Wow- Sot all catalytic activities exhibited by the
ever, the products from t,he S a + form n.re free of zeolites need be intracrystalline. For example.
branched-chain structures. with a n X zeolite of 4k.port size we have observed
Patdysis for the hydration of ethylene oxide to
TARLE r ethylene glycol and polyglycols with no hindrance
W D E C A N E (:R.4CKIXG. 3 HR. ~ P E H A T I O N , 470”, T = effect of port size in evidence. Herr the catalytic
9 SEC., 1 ATM. activity appears to be located at the euternsi surface
Iso- Tso- Olefins in of the crvstallites.
vo butane: pentane: crncketl
Decane n-butane n-pentano products. !n conventional surface catalysis the termination
Cntalytic S&I converted ratio rntio wt. Sr, ( t i a three-dimensional solid structure is considereci
Silica-alumina 25 3.1 3 0 37 to he the locus of actimty. For these zeolites, the
Na-aluminosilicate! X 32 0.0 0 0 62 concept of surface loses its conventional meaning
Ca-aluminosilicate, S 39 1. 1 2 4 30 and the molecular participants can find themselves
In contrast with its high catalytic activity for the exposed to unusual coulomb fields.
cracking of paraffins, the Na+ form is inact,ive for W t t wish to acknowledge contributions made X C I
the dealkylation of isopropylbenzene even a t 510’; various phases of the above work by fl. W. Maat-
however, the (:a++ form produces extensive conver- man, It. L. Golden, E. Mower, arid G ’f. Km-.
$ion a t 465‘. Alpha-pinene undergoes no reaction Socohiv ~ I O B OIL I L COUPANY, INC.
when refluxed with the Na+ form, but is converted l’AUL5BORO LABORATORIES P B. u EISZ
extensively to camphene by the Ca++salt. I’il’l \HORO, J. V J FRII,E~TF
The observed cracking activities are unexpected _ _ _ _ _ R r C L I V E D FEBRI‘ARY
25, 1qM)
because of the cwmmon view that acid it,^" is a (5) 1) W Brrch, rtl I 4 m Chpm Soc . 7 8 , i W t 3 tICLiF)
requirement arid the common experience o i poison-
ing by alkali and alkaline earth metals on con-
ventional si1ic:ious cracking catalyst~s.
We believe that the locus of catalytic activities THE NATURE OF THE SPECIES RESPON-
resides in the extensively developed interstkes of SIBLE FOR THE LONG WAVE LENGTH
the X crystai. These interstices are accessible to ABSORPTION BANJ IN ACIDIC
all molecules with critical diameters less than ea.
9A., Le., to ztll of t>hereactant and product mole- SOLUTIONS OF OLEFINS
rules described above. Sir:
We have heen able to demonstrate molecular- Distinc.tly different electronic spectra are ob-
shape-selective catalysis by utilizing intrinsic, t,ained from solutions of arylalkenes in .rmngly
catalytic activities described above. or artificially acaidic. and weakly acidic media. ‘rhus, while
inrorporat,ec.lc:Ltalytic materials within salt forms solutions of 1.1-diphenylcthylene (I)PE) in con-
: l i D. $4’. Brock, el d.,J . ilm. Chem. Soc., 78, XM3 ( I D X ) . rcntrated sulfuric acid exhihit only the spectrum
“2) R. X.Barrer. er ai., 7’rnn.v. Faraday Yor.. 63, 1 1 I 1 (1957).
(Amax. = 423 mp; e = 4.7 X IO4 pm.-I mole-’
‘3) Lindi, Air Prudiicts Co.. Tonawanda. New York.
‘ 4 ) E.@.. A . G. Ohlad, at al.. “.4dvances in (’atnlysis.” Vol. 1x1, liter) due to the expected methyldiphenylcarbonium
4cadernic I’rew New T o r k . N. Y . , 1951, PIX.199-L’&7. ion,’ solutions in weakly acid media. e.g., sulfuric-