November 1949

INDUSTRIAL AND ENGINEERING CHEMISTRY

(23) Thomas, C. L., and Ahlberg, J. E. (tcJ Universal Oil Products

Co.), U. S. Patent 2,229,353 (Jan. 21, 1941): 2,285,314 (June
2, 1942); 2,329,307 (Sept. 14, 1943).
5
(24) Thomas, C. L., and Bloch, H. 8. (to Universal Oil Products C o . ) ,
U. S. Patent 2,242,553 (May 20, 1941).
(25) Ibid.,2,333,903 (Nov. 9, 1943).
(26) Ibid., 1,416,965-6 (Mar. 4, 1947).
(27) Thomas, C. L., and Danforth, J. D. (to Universal Oil Products
Go.), U. 8. Patent 2,287,917 (June 30, 1942).
(28) Thomas, C. L., Hoekstra, J., and Pinkston, J. T.,J . Am. Chem.
Soc., 66,1694 (1944).

2573

(29) Voge, H. H., Good, G. N., and Greensfelder, B. S., IND.ENQ

CHEM.,
38, 1033 (1946).
(30) Whitmore, F. C., Chem. Eng. News, 26, 668 (1948).
(31) Whitmore, F. C., J . Am. Chem. Sec., 54, 3274 (1932).
(32) Whitmore, F. C., and StahIy, E. E., Ibid.,55, 4153 (1933).
RECEIVEDNovomber 15, 1948. This paper is taken from
which was part of a technioal information exchange ordered
ieum Administrator for War in Recommendation 41. The
formed at the Riverside, Ill., laboratories of Universal
Company.

a 1945 report
by the Petrowork was perOil Products

Catalytic and Thermal Cracking

of Pure Hvdrocarbons
J

MECHANISMS OF REACTION
B. S. GREENSFELDER, H. H. VOGE, AND G. M. GOOD
Shell Development Company, E m e r y d l e , Calif.
T h e primary cracking of pure hydrocarbons both with
and without catalysts has been studied in terms of the
distribution by carbon number of the cracked fragments
to allow arriving a t a mechanism of molecular disintegration. The secondary reactions of the cracked fragments have been followed by analyses of the product fractions to allow a further definition of the nature of the
cracking system. On the basis of this work, cracking systems are assigned to two fundamental classes; each class
is described by a set of characteristic reactions covering
both the primary cracking and the secendary reactions.
Correspondingly, two types of reaction mechanisms are
proposed, one a free radical (thermal type) mechanism
based on the Rice-Kossialroff theory of cracking, the
other a carbonium ion (acid-activated type) mechanism

derived from the work of Whitmore and others on the

properties of carbonium ion systems. Cracking catalysts
are available for either type of reaction mechanism;
those which accelerate free radical type reactions are nonacidic, and those which accelerate carbonium ion type
reactions are acidic. Commercial acid-treated clay and
synthetic silica-alumina cracking catalysts belong to the
latter class. Activated carbon, a highly active, nonacidic
catalyst, gives a unique product distribution which is
explained as a quenched free radical type of cracking.
Activated pure alumina has weakly acidic properties and
produces moderate catalysis of both types of reaction
mechanism, the primary cracking corresponding to a free
radical mechanism and the secondary reactions of product
olefins following a carbonium ion mechanism.

mental unity is thus established for a number of important hydrocarbon catalytic reaction systems.
Thermal cracking and cracking over nonacidic catalysts have
also been studied. Mechanisms are also proposed for these
systems for comparison with those of the industrial or conventional catalytic cracking process,
Despite the wide variety of products obtained in the cracking
of different hydrocarbons either thermally or by any catalytic
process, i t has become increasingly evident that certain characteristic severances of carbon-carbon bonds and secondary reactions of olefins are always obtained thermally and over certain nonacidic catalysts, whereas another set of reactions prevails
consistently in the presence of acidic oxide cracking catalysts.
The principal contrasting reactions are shown here with respect
to specific hydrocarbons or hydrocarbon types which have been
tested. Comparisons between classes refer to hydrocarbons
with the same number of carbon atoms (Table A).
Both the hydrocarbon class and the isomeric form of a given
hydrocarbon control the primary products obtained. Because
of uniformity and simplicity of structure, normal paraffins (and
olefins) were given preferred study. The use of a relatively
large aliphatic hydrocarbon assists identification of important
secondary reactions because of its extensive fragmentation.

RIOR work on the catalytic cracking of pure hydrocarbons

has led t o a general characterization of the rates of cracking
and product distributions of the principal classes of petroleum
hydrocarbons (10-13). I n addition, a number of secondary
reactions of olefins have been investigated and the effects of
structural isomerism on the rates of cracking of several types
of hydrocarbons were examined (9,54). Consistent mechanisms
of reaction are now proposed, based on the primary hypothesis
that any hydrocarbon reacting over this type of catalyst is transformed into a carbonium ion (33,which then cracks or undergoes
secondary reactions according to definite rules. This hypothesis
is directly coupled with the requirement that the acidic oxide
type of cracking catalyst must make available reactive positive
hydrogen ions (protons) capable of producing carbonium ions
on contact with the hydrocarbon feed. A similar type of approach was proposed independently by Thomas (52).
The properties of carbonium ions, which are postulated to
represent the reactive form of the hydrocarbon in conventional
catalytic cracking, also determine the mechanism of reaction and
the type of product in many other acid-catalyzed hydrocarbon
reactions, such a8 the isomerization, polymerization, parafKn
alkylation, and hydrogen transfer reactions of olefins, the isomerization of paraffins, and the alkylation of aromatics. Funda-

INDUSTRIAL AND ENGINEERING CHEMISTRY

2514

Therefore, much study was devoted to the cracking of n-hexadecane (cetane), a representative normal paraffin in the gas-oil
boiling range.
TERMINOLOGY
AND PROCEDURE.
The definitions and terminology used here correspond to those in a previous paper (10);
extent of cracking, conversion, and percentage decomposed are
used interchangeably t o include gas, liquid boiling below the
original, and coke-redefined (34) t o include carbon and hydrogen-all summed on a no-loss basis (9).
T h e apparatus and procedure used in this work have heen
described (9, 15) with certain modifications for thermal craclcing experiments (33); analytical methods have been amplified
t o include deteimination of paraffin isomers by infrared and
aromatics by ultraviolet spectrometry. Liquid products from
aliphatic feed stocks were fractionated by carbon number
(9); those from other hydrocarbons were separated into distillxte
fractions comprising significant boiling ranges.
THERMAL CRACKING

Vol. 41, No. 11

the amount of ethylene, but i t still reniains the major product.

By successive recracking, the radicals ultimately are reduced t o
methyl or ethyl fragments. These radicals then react with feed
stock molecules t o produce new fIee radicals and are themselves
converted t o methane or ethane. Thus, cracking is propagated
ass a chain reaction. T o start the chain and to compensate for
the loss of chain carriers by side reactions, it may be assumed
t h a t a few highly activated molecules decompose spontaneously
or a t the wall.
The R-K theory also concerns the manner of formation of a
iadical fiom the original paraffin. .;2 primary hydrogen atom is
more securely bonded and is removed less readily than asecondary
hydrogen atom, and a numerical value of 2000 calories is assigned
as the difference in activation eneigies, which corresponds to a
relative rate of removal of 1 to 3.66 a t 500" C. Tertiary hydrogen
is still more easily removed, 13.4 times as fast as primary hydrogen, but this does not enter into the cracking of normal paraffins, since no skeletal isomerization appears to take place. Radical isomerization presumably occurs through a coiled configuration of a single radical, in which the hydrogen donor and acceptor
carbon atoms must closely approach each other. This last restriction affects the calculations for cetane vcry littlc ( 3 3 ) .
A schematic representation of cetane cracking IS as follows:

The most successful present explanation of thermal cracking of

hydrocarbons is the Rice free radical theory (2b-27) as modified
b y Kossiakoff and Rice (19). This will be called the "RKtheory" and is summarized from another paper (33) as follows
to explain the cracking of a normal paraffin:
1. Small radical, such as CH8, from prior cycle or from initial
The normal paraffin molecule loses a hydrogen atom by collihydrocarbon rupture, combines with an I1 atom in cetane to give
sion and reaction with a small free hydrocarbon radical or a free
a cetyl radical and methane:
hydrogen atom, thereby becoming a free radical itself.
H H I1 H H H H I H H H I H H H H
This radical may immediately crack or may undergo
CHa
HC -C-C-C-C-C-C-C-C-C-C-C-C-C-C-CH
radical isomerization prior to cracking. Radical isomI H H . H H H H H H H H H H H H
erization is a change of the position of a hydrogen
2. Cetyl radical cracks beta to free valence t o give, say, n
atom, usually to yield a more stable radical. Cracking of
pentene-1 and undecyl-1 radical:
either the original or isomerized radical then takes place a t a
carbon-carbon bond located in the beta position t o the carbon
H H H H H
H H H H H H H H H H H
atom lacking one hydrogen atom. Cracking at the beta posiHC-C-C-C=C
and C-C-C-C-C-C-C-C-C--C-CH
H H H
H
H H H H H H H H H H H
tion gives directly an alpha olefin and a primary radical
(lacking one hydrogen atom on a primary carbon atom); in this
3. Undecyl-1 radical cracks beta to free valence t o give ethylstep there is no change of position of any hydrogen atom with
ene and nonyl-1 radical; repeat process t o give ethylene and
respect t o the carbon skeleton.
heptyl-1 radical; repeat process to give ethylene and amyl-l
radical; repeat process to give ethylene and propyl-1 radical;
The primary radical derived from this step may immediately
repeat process t o give ethylene and methyl radical, which then
recrack a t the beta bond t o give ethylene and another primary
reacts as in step 1 t o continue the chain reaction.
radical, or i t may first isomerize. I n the absence of radical isomn4. Alternatively, some of the radicals in step 3 may isomerize
erization, only primary radicals are derived from the cracking
to secondary forms, for example,
reactions of normal paraffins; primary radicals thus give only
H H H H
ethylene as the olefinic product. Radical isomerization rrduces
HC-C-C--C--R
H . H H

TABLE
A
Hydrocarbon
n-Hexadecane
(cetane)
Alkyl aromatics
Normal olefins
Olefins

Iiaphthenos

'

Thermal Cracking
Major product is CP with
much C i a n d Ca; much Ci
to CIS n-a-olefins. few
branched sliphatiis
Cracked within side chain
Double bond shifts slowly;
little skeletal isomerization
Hydrogen transfer is a
minor reaction and is
nonselective for tertiary
olefins
Crack a t about same rate
a s corresponding pariaffins
Crack a t lower r a t e t h e n
paraffins

Catalytic Cracking
Major product is Ca to Cs;
few n-a-olefins above
C4; aliphatics mostly
branched
Cracked next to ring
Double
bond
shifts
rapidly: extensive skelet a l isomerization
Hydrogen transfer is a n
important reaction and
is selective for tertiary
olefins
Crack a t much higher rate
than
corresponding.
paraffins
Crack a t about same rate
a s paraffins with equivalent etructural groups

Crack a t lower r a t e than

paraffins

Crack at higher rate than

paraffins

Small amounts of aromatics

formed a t 500 C.

Large amounts of aro;

matica formed a t 500
C.

(9)

Alkyl aromatics
(with propyl
or larger substituents)
Aliphatics

~~

~~

~~

~~

~~

which gives propylene on cracking beta to the free valence. The

final radical in either step 3 or 4 may be ethyl instead of methyl,
which also reacts as in step 1t o continue the chain reaction.

CRACKING
OF CETANE,
CETENE,PARAFFIN
WAX, AND ISODOThe authors' work on the thermal cracking of cetane
a t 500 C. and 1 atmosphere gave the products shown in Table I,
columns 1 and 2 (with quartz chips as inert filler in the rpactor),
as repeated in simplified form from another paper (33). The
agreement with the product distribution worked out by the rules
of the R-K theory (33) is considered good. To summarize,
long normal paraffins crack thermally to give ( a ) the complete
sequence of normal alpha olefins (899); ( b ) large amounts of
ethylene and propylene by successive beta cracking of the resultant primary or isomerized radicals; and (e) fairly large
amounts of methane and ethane as end products of radical d e
composition. Of great importance is the absence of secondary
reactions, especially of olefins. Considerable weight may be
placed on the results (23)of cracking a paraffin wax (averaging
n-Cz6Hsa)
as further evidence for the rules cited here. The products corresponded with those expected from the R-K theory,
and of particular interest were the liquid fractions, Ce to Cia,
which were about 90% olefinic by bromine number.
UECAXE.
O

November 1949

+3

INDUSTRIAL AND ENGINEERING CHEMISTRY

From Gault (8) the over-all product distribution from the

thermal cracking of cetene a t 450 to 550 C. (11)closely resembles
that from cetane. The first order cracking rate constants are
also similar, Keetane = 0.003 (33) and Koetene = about 0.007
second-1 (11,recalculated from 8) a t 500' C.; this demonstrates
that the double bond has no large effect on either the mechanism
or rate of cracking.
For further verification of the R-K theory, the product distribution was calculated by the authors (33) for isododecane
(presumably chiefly 2,2,4,6,6-~entamethyIheptane),
which cracks
very differently from its isomer, n-dodecane (Table V of 10).
As may be seen in another work (33) the correspondence of the
calculated and experimental results is considered fairly good in
view of the complex structure of this hydrocarbon and the
approximate nature of the parameters used in the R-K theory.
CRACKINGOF NAPHTHENESAND AROMATICS.Naphthenes
and aromatics are of much importance in petroleum fractions.
Most of these cyclic hydrocarbons in petroleum are alkyl substituted; their cracking behavior is determined by the combined
effect of the cyclic group, the alkyl groups attached thereto, and
the nature of the bonds linking the side groups to the ring.
D a t a on the thermal cracking of pure naphthenes are scanty;
Decalin (30) appears to crack like a branched paraffin, accompanied by ring dehydrogenation to aromatics. The available
data lead to the conclusion that aromatic production via dehydrogenation is an important reaction of cyclohexane type naphthenes,
but t h a t otherwise there is no departure from the general prin-ciples of the R K theory implied in the observed results. Information is lacking on the liquid products of thermally cracking
cyclopentane type naphthenes, which cannot dehydrogenate to
aromatics without prior ring isomerization. One publication
(18) indicates t h a t scant aromatics came from cyclopentane or
methylcyclopentane.
Aromatic rings are stable under thermal cracking conditions.
Therefore, the cracking of petroleum aromatics is essentially
confined t o the cracking of attached carbon chains which
may be alkyl or cycloalkyl groups, or naphthenic portions
of condensed ring systems. These chains may be expected to
tend t o crack within themselves in accordance with the rules of
the R-K theory. I n thermal cracking, there is considerable
reluctance to crack a t the bond next t o the aromatic ring. Thus,
n-propyl and isopropyl benzenes give chiefly toluene and styrene,
respectively ( 5 ) .
CATALYTIC CRACKING

The study of the catalytic cracking of pure hydrocarbons was

undertaken to explore the chemistry of the industrial process.
The present commercial catalysts are effective agents for accelerating those cracking and secondary reactions which lead t o a
product distribution of considerable economic value t o the
petroleum refiner. The majority of the authors' published experiments have been made with a synthetic silica-zirconiaalumina catalyst designated as UOP cracking catalyst Type B;
this has virtually the same cracking characteristics as the synthetic silica-alumina catalysts in general commercial use. Catalysts prepared from natural clays, such as acid-treated Californian bentonitic montmorillonite, give a fairly similar product
distribution and are also in commercial use.
I n general, the statements regarding acidity of porous solids
made herein rest on the findings of Tamele (31)which are supported by the work of Thomas (32)and refer particularly to the
type of acidity denoted by the term "proton availability";
this means t h a t protons (hydrogen ions) are present and available
for reaction with even weak bases and with suitable hydrocarbons.
This acidity is measured not only as pH of the material in contact with water, but also by the reaction of the dry solid with
ammonia, a basic gas. On the whole, good qualitative correspondence between acidity so considered and catalytic cracking
activity has been established.

2515

AND OBSERVED
PRODUCTS
IN THE
TABLE
I. CALCULATED
THERMAL
AND CATALYTIC
CRACKING
OF CETANE

(Temperature, 500' C.; pressure, atmospheric)

Quartz
Activated Carbon
UOP-B
Run
C-590
C-708
C-579
L.h.s.v.a
...
0.05
. ..
10.0
..
10.0
Conversion, wt. %
'
31.5
..
26.6
... 2 4 . 2
Moles product/100
Calcd. Obsvd.
moles cracked
Calcd. Obsvd.
Calcd. Obsvd.
61
53
4"
11
c1
0
5
139
130
13
22
0
12
CZ
50
60
21
23
Ca
95
97
27
23
17
17
C4
97
102
15
9
20
13
CS
72
64
17
24
Ce
13
21
50
41
14
16
13
15
7
8
C7
12
13
13
9
C8
6
8
11
10
I3
18
5
3
CS
10
11
13
15
c10
4
3
9
9
13
14
4
2
CII
8
7
17
13
4
2
c12
8
4
7
CIS
21
7
2
7
5
C,A
-..
_12_
CIS
4
4 1 4
0'
...
Total hydrocarbon
378
' - 200
223
339
358
26
0
Hydrogen
0
17
0
12

.. .

. ..
.

...

..T

. . ..

"1

- -

Liquid hourly space velocity.

Extensive work has been carried out under the direction of

Tamele in t h e colloid chemistry department of these laboratories
on the relation of acidity to the cracking activity of porous solids
( 3 1 ) . This work has been of essential importance to the development of the present theories of reaction mechanisms over such
catalysts in terms of carbonium ions, which require available
protons for their creation. It was demonstrated t h a t pure porous
silica, although derived from silicic acid, had no cracking activity
and had no available acidity. On the other hand, small amounts
of alumina properly added to pure silica endowed the latter with
considerable activity. This result was traced t o the presence
of available protons in the combined silica-alumina structure,
which structure so distributes the valence charges of aluminum,
silicon, and oxygen atoms that additional cations are required t o
obtain electrostatic neutrality. Thus, protons are incorporated
into the structure when such materials are prepared in an acid environment, and those protons which are available a t the surface are
readily exchanged for other cations such as sodium. The latter
render the catalyst inactive since no carbonium ions can then be
formed. This behavior places these solids in t h e class of baseexchange agents, a property common to conventional cracking
catalysts, both synthetic and natural.
Definite experimental evidence has been obtained by Tamele
(SI) for the strongly acidic character of silica-alumina, silicazirconia-alumina (UOP Type B cracking catalyst), and acidtreated clays. Puve silica has been shown to be nonacidic. The
activated carbon used in t h e present experiments has no indicated proton availability and shows an alkaline reaction in water;
i t is also classified here as a nonacidic catalyst. The pure alumina used by the authors has been determined to be aweaklyacidic
catalyst, a classification which fits well with many circumstantial
observations on its properties, manner of preparation, and catalytic activity.
To extend our knowledge of cracking reactions, experiments
have now been made by the authors with pure silica and pure
alumina of high surface areas, both of which accelerate the rate
of cracking of most pure hydrocarbons with respect to the thermal
rates observed over quartz chips. I n addition, the authors have
made comparable experiments in some extensiveness with activated carbon of very high indicated B-E-T (Brunauer-EmmettTeller) ( 4 ) surface area, because of the unique product distribution' obtained with this material. The several catalytic agents
will be discussed in approximate order of their transition from
thermal to acid type of cracking. Throughout the text the relative activities of the catalysts for the cracking of pure hydrocarbons are computed by either of two methods, the preferred being
the ratio of molal flow rates required for equal extents of cracking,

INDUSTRIAL AND ENGINEERING CHEMISTRY

2576

OF EXTENTS
OF CRACKING
ovan PVRE
TABLE
11. COXPARISON
SILICAGEL, QUARTZCHIPS, A N D UOP-B C A T A L Y ~ T

(Process period, 1 h o w ; preqsure, atmospheric)

Flow R a t e
Amt. Cracked, K t . %,
Temp.,
Moles/
Pure
Hydrocarbon
O C.
L.h.s.v.a
l./hr,
Silica Gel Quartz UOP-Rb
Cetane
500
0.5
1.7
20.9
oa.6
80
550
4.2c
27.2
Decalin
0.6
0.3
40
450
4.2C
27.2
n-Octenes
0.8
...
45
Cumene
500
'
3.8
27.2
0.3
1.1
80
hourly space velocity.
* Liquid
Estimated from d a t a a t other flow rates.
4pproxi.natelp.

a
C

TABLE
111. CRACKING O F CETANE OVER
QUARTZ
CHIPS

PURE

SILICA GEL

.\VU

(Temperature, 500'

C.; pressure, atmospheric)

Pnre
Qnartz
Silica Gel
Chips
C-930
C-590
Run
Conversion, mt. %
20.9
81.6
0 5
0 06"
Liquid hourly spare velocity
Process period, min.
60
270
Moles product/100 moles cracked
35
53
C1
104
130
C?
57
60
CS
23
30
C4
Cracking Surface ,

19

C6

18
14
15

C8

c7
C8

10

CP
Cro

7
10

c
1
1

C1e
C..,.?
Cl4

9
24

18
13

10
11

ClS

Total hydrocarbon
Hydrogen
Olefin content of fractions, wt. To

c,
GS

42-74O C.
196-217'C.
Aromatic content of fractions. mt. %
42-99' C.
99-125" C.
Iso/normal utylenes ratio

70
92
95
97

0.7
0.08

78

nrc

90
, .

3
0.07

The flow rate for t h e thermal run is based on t h e total volume a t 500' *
bo C. occupied by quartz chips. Tho hot free space was found to be roughly
45% of this volume. The flow rate for silica gel, as with other catalysts,
is based on t h e total catalyst volume, all of which was a t 500' i. 5' C .

and the other the ratio of exten's of cracking a t equal flow rates.
The activity of a cracking catalyst, such as the silica-alumina
type, may change rapidly with time; the values cited here are
those obtained for process periods of 15 minutes t o 1hour.
PURE
SILICAGEL. Pure silica gel has little catalytic cracking
activity, but the addition of very small amounts of alumina, even
a few hundredths of one per cent, will raise the activity of pure
silica gel t o a high value (7, 31). The addition of more alumina
(about 10 t o 15%) makes a highly active and stable cracking
catalyst, as represented by present commercial production of
synthetic silica-alumina catalysts in this country.
T o test t h e cracking properties of pure silica gel containing less
than 0.01% by weight of alumina and with a specific surface of
531 square meters per gram, the authors used cetane. The
results are shown in Table I1 together with data of Tainele (3'1)
for t h e cracking of three other pure hydrocarbons, all compared
over pure silica gel, quartz chips, and UOP-B catalyst.
I n comparison with UOP-B catalyst, the relative activity of
pure silica gel was very low. However, this latter material
catalyzed the cracking of cetane by increasing t h e rate several
times relative t o the rate over quartz chips. Table I11 shows a
sixfold increase. Therefore, product distribution is of paramount
interest for ascertaining the mode of cracking.
Virtually t h e same product distribution is obtained in both
cases (Table 111). The lower amounts of C1 and CZ over pure

Vol. 41, No. 11

silica gel represent a difference of less than 5$Z0 of the cetane

cracked. It is concluded t h a t cetane cracks over pure silica gel
by the same mechanism as over quarts chips-namely, via free
radicals according t o the R-K theory. The increased rate is
attributed to the high surface area of the silica gel, which suggests
that free radical formation may be assisted a t a suitable solid
surface.
ACTIVATEDCARBOX. Steam-activated carbon from coconut charcoal, of 1600 square meters per gram specific surface,
has given the authors results with cetane remarkably different
both in cracking rate and product distribution from those observed thermally and over silica-alumina type catalysts. Cetane
cracked from one to ten times as fast over activated carbon as
over UOP-B catalyst, depending on the extent of cracking' this
is equivalent t o a t least fifty times the thermal rate. The product
distribution is shown in Table I in comparison with t h a t obtained
thermally over quartz chips, a t a comparable extent of cracking.
The cracked products from C1 to CIS are seen to be rather evenly
distributed over the entire range. I n comparison with thermal
cracking, 155 moles less hydrocarbon were obtained per 100 moles
cetane cracked; this difference can be assigned principally to
the smaller production of CI, Cf, and CB,inclusive, which is less
by 187 moles. Indeed, little more than 2 moles of product were
obtained per mole of cetane cracked over activated carbon in
this experimenb. Very little chain-branching was noted, and
the product contained more paraffins than olefins throughout the
entire range. Over half of the normal olefins examined (C8,
Cp, and CIZ)were alpha isomers.
From these observations the authors have concluded that a
carbonium ion mechanism could not explain the results. T h e
high normal alpha olefin content and the lack of skeletal isomerization of olefins correspond to the thermal or free radical (R-K)
mode of cracking, but the relatively high saturation of the product (over 60'%) throughout the whole range and the lack of
preferential formation of CI, Cp, and CBdo not. T o solve this dilemma, the authors have proposed that t h e cracking may start
via free radicals and therefore should show the effect of different
ty-pes of carbon-hydrogen bonds on the rate of cracking as postulated by the R-K theory. This was tested with the five hexane
isomers, as reported later in the text; the authors have obtained
reasonably good agreement with experimental data by using the
R-K values for the relative reactivities of primary and secondary
hydrogen atoms. A slightly lower value for tertiary hydrogen
is derived from the hexane tests but is not needed for the cetane
calculation.
Accordingly, the cracking of cetane over activated carbon may'
be explained as follows:

A free radical is formed a t the catalyst surface by the removal

of a hydrogen atom anywhere in the carbon chain, as in the R-K
theory, and this radical cracks at the beta position, also according
t o R-K theory, t o yield a normal alpha olefin and a primary free
radical. This primary radical is rap dly saturated or quenched
by the addition of a hydrogen atom a t the surface of the catalyst
to form the corresponding normal paraffin which cracks no further
unless it has high molecular weight (see discussion of n-CdT64).
On the basis of these simple assumptions, t h e authors calculated the product distribution shown in Table I, wherein encouraging agreement with t h e experimental results is found.
Cracking over activated carbon may thus be characterized as a
radjcal mechanism at an active surface, which later enables
hydrogen atoms t o combine with radicals from the first cracking
step and thereby prevents their further cracking to small fragments.
T h e great acceleration of cracking observed with cetane may
be ascribed t o the characteristics of the high surface area of the
activated carbon, nrhich acts (a)t o remove hydrogen from the
hydrocarbon to generate reactive free radicalq; and conversely
( b ) to return hydrogen t o the radical derived from the cracking
reaction t o convert it t o a normal paraffin. T h e saturation

November 1949

INDUSTRIAL AND ENGINEERING CHEMISTRY

2577

activated carbon proceeds by a free radical, rather than a carCRACKING

OF PURE
HYDROCARBONS
OVER ACTIVATED bonium ion mechanism.
CARBON
An important postulate in the R K theory is t h a t of the
(Temperature, 500 C.; pressure, atmospheric)
different reactivities of the three types of hydrogen-carbon bonds
Compound
Chief Products
Run
(primary, secondary, and tertiary) in aliphatic hydrocarbons.
Fairly even distribution of CI t o Cia
C-708
Cetane
At 500" C., these are given as 1.0,3.66, and 13.4, respectively (19).
products,
with
high
liquid/gas"
C-721
Cetene
If the first (and rate-controlling) step in catalytic cracking over
ratio
Methane
a
n
d
ethylbenzene
C-686
Cumene
activated carbon is the removal of a hydrogen atom, then these
Hydrogen a n d naphthalene
C-722
Decalin
reactivities should be reflected in the rates of cracking of struca CI t o C4, inclusive.
tural isomers. The authors therefore cracked the five hexane
isomers over activated carbon, with the result t h a t the secondary/
TABLEV. CATALYTIC
CRACKING
OF HEXANEISOMERS
OVER
ACTIVATED
CARBON
primary reactivity ratio of 3.66 was confirmed t o within 4% by
(Temperature, 500" C.; pressure, atmospheric; process period, 1 hour;
the data for normal and neohexane, which contain only these
flow rate, 7.1 moles/l./hr.)
two kinds of bonds. For tertiary hydrogen, a value of 11.0
Ratios of Cracking Rates
was computed from data on 3-methylpentane with respect to
Hexane Isomer
Calculated
Observed
n-hexane. With this value, fairly good agreement was obtained
NeohexnnR
0.56
0.54
0.98
1.08
2,3iDimethylbutana
for the rate of cracking of 2,3-dimethylbutane, as shown in
1.00a
1.00b
3-Methylpentane
Table V; 2-methylpentane fell out of line. Considering the good
1.00
1 27
2-Methyfpentane
1:02b
1.02
n-Hexane
agreement in four out of five cases, i t seems quite believable
a Assigned value of unity.
that removal of a hydrogen atom is the initial step in catalytic
Experiments used t o determine *he rate ratio of tertiary to primary
hydrogen removal.
cracking over activated carbon.
Another test of the proposed mechanism is the prediction of
cracked products from the isomeric hexanes, which represent
of total aliphatic products above the theoretical 50% may be
many different carbon-carbon groupings within small paraffin
correlated with the observed activity of this catalyst for hydrogen
molecules. Applying the relative rates of removal of 1, 3.66,
transfer, a property which falls in line with the reactions noted
and 11.0 for primary, secondary, and tertiary hydrogen atoms,
above. Normal p a r f f i s , C,, larger than cetane should yield
the beta fission rule, and the postulate for activated carbon that
some amount of normal paraffins and olefins of 16 t o n - 1 carbon
radicals from the first cracking step are resaturated t o paraffins
atoms under the conditions just given. These products should
and not recracked, fair agreement with the experimental rethen extensively recrack. The authors found this t o be exactly
sults is obtained here, as depicted in Table VI. These calcuthe case for a Borneo wax of approximate average formula nlations offer further confirmation of the suggested mode of
CzsH54, which yielded 363 moles of hydrocarbon product per 100
cracking over activated carbon, especially in view of the possible
moles wax cracked at 44y0 conversion (run C-715) in these experidisturbing effects of different carbon atom groupings arranged
ments. Recracking of most of the material above Cla is indiin such close proximity t o one another in the hexane isomers.
cated. The 2 t o 1 mole ratio of hydrocarbon product to cracked
PUREALUMINA. Porous alumina in various forms, such as
feed stock which was approached by cetane represents the lowest
bauxite or precipitated alumina, is an important type of catalyst
possible value of this ratio.
either alone or in combination with other substances. When
To characterize further the catalysis over activated carbon, the
mixed with small amounts of silica, many aluminas acquire the
authors tested four other hydrocarbons. The chief products
cracking properties of the commercial silica-alumina catalyst
from cetane, cetene, cumene, and Decalin are shown in Table
to some degree (20). T o observe the behavior of a pure alumina,
IV. Cetene cracked a t about the same rate as cetane. I n cona sample prepared by the authors containing below 0.01 yo by
trast, cetene cracks far faster than cetane over acidio catalysts.
weight silica with specific surface 180 square meters per gram
The cracked products were similar to those from cetane, although
was teated with cetane and cumene.
somewhat less saturated (about 55% unsaturation of the aliThe authors found that cetane cracked a t about half the rate
phatics). This considerable saturation of product from an oleover pure alumina as over UOP-B, with t h e comparative product
finic feed stock may be correlated with the simultaneous producdistribution shown in Table VII. The amount of each comtion of aromatics. (The release of hydrogen by aromatic formaponent is intermediate t o t h a t obtained over UOP-B and actition may also enter into the excess saturation-60yo instead of
vated carbon, with the exception of CI, Cz, CS,and C6. I n each
theoretical 50y0'o--of the products from cetane cracking, but does
of the latter cases the value is closer t o that for activated carbon
not alter the concept of radical saturation a t the carbon surface,
than to the value for thermal cracking.
whatever the source of the hydrogen may be.) Cumene gave
Cumene was cracked about 10% at 500" C. and 1.9 liquid hourly
methane and ethylbenzene, the same bond division as in thermal
Bpace velocity, compared with about 1% over quartz chips or silica
cracking but accompanied by saturation of the vinyl side chain,
gel, 8% over activated carbon, and 84% over UOP-B. The
Decalin was dehydrogenated t o naphthalene and showed a 200gas composition indicated a much higher ratio of Cs to methane
fold acceleration of this important thermal reaction, which
than for thermal or activated carbon cracking, but considerably
demonstrates the high dehydrogenation activity of activated
lower than for UOP-B. Since removal of the entire alkyl group
carbon. These observations support the view t h a t cracking over
as propylene is characteristic of acid type cracking, and the production of methane and CS aromatics is found
thermally (6) and over activated carbon, an interTABLE
VI. CATALYTIC
CRACKING
OF HEXANE ISOMERS
OVY~RACTIVATED mediate type of cracking is evident, both with reCARBON
spect t o rate and product distribution.
(Temperature, 500n C.; pressure, atmospheric. process period, 1 hour; flow rate, 7.1
The authors have concluded from the foregoing
moles/l./Lr.)
t
h
a
t this weakly acidic pure alumina displays
3-Methyl2-Methyl2,a-DimethylCracked
a mixed type of cracking, intermediate t o t h a t
products,
%-Hexane
Neohexane
pentane
pentane
butane
.\%ole% Obsvd. Calcd. Obsvd. Calcd. Obsvd. Calod. Obsvd. Calcd. Obsvd. Calcd.
over strongly acidic oxides and activated carbon,
CI
15
5
27
28
25
21
13
13
36
37
with perhaps some accelerated thermal cracking
cz
28
24
33
22
29
29
22
20
3
0
cs
35
42
7
0
10
0
39
34
20
26
entering to a small degree. The butylenes and
c
4
17
24
28
22
24
29
21
20
12
0
amylenes were found t o be skeletally isomerized
C E
5
5
5
28
12
21
6
13
19
37
to equilibrium; this demonstrated the existence of

TABLE
IV.

INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY

2578

TABLE
VII. CRACKING
OF CETANEOVER PCREh . v > I I X . 4

AND

OTHER CATlLYsTs

(Temperature, 500" C.; pressure, atmospheric)

Catalyst or surface
Alumina UOP-B Carbon
C-587
C-710
C-931
Run
Liquid hourly space velocity
0.5
1.0
3.9
6
8
.
0
68.4a
Conversion. wt. 70
61.7
moles cracked

29

44

58
53
22
11

15

11
12
11

A
3

50

32
7
5
5

4
3
2
1

13

26

28

26
28
16

24
13
20
16
10
14
7
4
4

53
130

60
23
9
24
16
13

10

11
9
7
8
5

206

,..

247

...
-

199

12

16

17

Total hydrocarbon
Hydrogen

11
18
116
113

Quartz
C-590
0.05
31.5

367

378

Does not include coke.

some carbonium ion or acid type activity. The observed data

may be correlated with the relatively weak acidity arid high surface area of the pure porous alumina.
The large amount of hydrogen produced in cetane cracking can
be partially attributed t o the rat,her low hydrogen transfer activity, as suggested by the high butenes to butanes mtio, coupled
with considerable dehydrogenation activit,y t o form aromatics
(as observed) and t o release molecular hydrogen. Anot,her
contributing factor t o high hydrogen production might be the
stabilization of some of the free radicals from the first, craclring
step by the removal of a second hydrogen atom to form an olefin
and a n adsorbed hydrogen atom a t the surface of t h e catalyst,
in contrast t o the addition of a hydrogen atom to form a paraffin, as in t h e case of activated carbon. Then the weak acidic
character of the pure alumina Tvould come into play and encoursge the cracking of the resultant large olefins according t o the
carbonium ion mechanism t o be proposed for acidic oxide catalysts. These latter catalyst's have much greater activity for
cracking olefins than for cracking paraffins. I n proper balance,
such a mechanism can account for a product distribut'ion for
cetane over alumina intermediate to those observed over activated carbon and UOP-B catalysts.
ACIDIC OXIDE CATALYSTS.Industrial cataly-tic cracking of
petroleum fractions utilizes porous solid acidic oxide cat'alystsfor example, synthetic silica-alumina gel with 10 t o 15% by weight
alumina and specific surface area ranging from 250 t o 600 square
meters per gram. Most of our experiments have been made with
a synthetic gel catalyst of virtually the same cracking characteristics-namely, UOP Type R, which analyzed 86.2% silica, 9.470
zirconia, and 4.3y0alumina, and which had specific surface about
330 square meters per gram.
The behavior of over sixty pure hydrocarbons in t h e presence
of this catalyst has beon reported (9-13,34.). A comparison n-ith
thermal (free radical-type) cracking \-,-as made earlier in the
paper, and i t has been proposed here t h a t cracking over the
nonacidic cat'alysta, pure silica gel, and activated carbon can be
explained as t h e simple acceleration of thermal free radical-type
cracking for t h e former and as an accelerated but modified,
quenched free radical-type cracking for the latter. Cracking
over porous solid acidic catalysts appears to comprise a process
of a very different kind, closely allied t o those hydrocarbon reactions which always require the presence of an acidic catalyst
but which can occur a t lower temperatures. Acidic catalysts
exist in many forms, including solid heteropoly acids, solid aluminum chloride with various promoters and supports, liquid sulfuric,
phosphoric, borofluohydrjc, and hydrofluoric acids, aqueous solutions of the foregoing, liquid organic complexes with aluminum

Vol. 41, No. 11

chloride, porous solids impregnated with acidic substances, acidtreated clays, and acidic mixtures of refractory oxides, such as
t h e present commercial cracking catalysts. These substances
all regisler acidity intrinsically or in contact with water and can
be viewed a s the source of t h e protons required to convert hydrocarbons into reactive carbonium ions.
CARBONIUM
IONR E A C T I O ~ ST. h e common features of these:
acid-catalyzed hydrocarbon reactions are the attack on the hydrocarbon, the production of a carboniuni ion, and the behavior
of carbonium ions according t o specific rules (36). Somo of
these rules are reviewed here for the sake of exposition of the concepts t o be applied t o catalytic cracking. The formation of a
carbonium ion from a hydroca,rbon may occur in several different,
ways. I n general, unsaturates add a proton t o form a carbonium
ion, and saturates lose a hydride ion t o form a carbonium ion
(36). The authors believe t h a t protons ( H + j , hydrideions (H-j,
and carbonium ions ( R + )in the catalytic systems under discussion
are always associated with, and are t,ransferred t o and from, complementary electronegative or electropositive atoms, groups,
molecules, or catalyst surface regions. The carbonium ion can
be regarded as a simplified concept of a polarized state, but a
concept which usefully predicts reactions according to a definite
set of rules. These rules serve to emphasize the close relation
of catalytic cracking t o many ot,hcr acid-catalyzed hydrocarbon
reactions. T o give subst,aiice and example t o these concept,si,
t h e simplest and best-known set of reactions, involving the addition of a proton t o a n olefin, will be discussed next.
Olefins: A proton will combine with an olefin by taking the
two Pi electrons from the ethylenic double bond to form an
ordinary hydrogen-carbon bond comprising one pair of electrons
(36). This bond will be made with one of the h o carbon atoms
sharing the original double bond; the other carbon atom will
now carry a positive charge and may be designated the "carbonium ion carbon atom," as will be shown.
For a symmetrical olefin, two equivalent struct,ures a r ~017tained :

+ >C=C<

+ >c-c<

IT-+

:111d

>c-<r<
+

I3

I n the case of unsymmetrical olefins, the proton Trill generally

add preferentially to one of the two ethylenic carbon atoms;
this has recently been given quantitative expression by Evans
and I'olnnyi ( 6 ) , from bond energies a.nd ionization potentials.
They give t,he proton affinities (Pi) of the first rind swond carbon
atoms as follows, x i t h PIand P1 in kg.-cal.:
Olefin
HIC=CH2

H,C= C "ICHa
HzC=C(CHa)z

PI

152
178.5
189

Pz
152
168.5

108

Resultant,

Ethvl

ser-Propyl

teit-Butyl

Ions
Ethyl

n-Propyl
iso-Butyl

Thus, sec-propyl ion is favored over n-propyl ion by 7 kg.-cal.;

tert-butyl ion is favored over isobutyl ion by 21 kg.-cal. These
relative energy values are in accord with the modes ol formation,
rearrangement, and dissociation of carbonium ions, as well as
with t h e manner of their addition l o nucleophilic moleculc~ssuch
as olefins and aromatics. Furthermore, these values give quantitative expression to Markownikoff's rule.
These relations easily account for the important catalytic
cracking secondary reaction of' olefin double bond shift studied
by t h e present authors ( 3 4 ) . T o illustrate:

IT,C=CEI--CII*-CH1
H
Hac-CII--CH~-CII,

--+

+H&-CH=CII-CIIa

+ H'

in accordance with the lesser proton affinity of middle carbon

atoms in most olefins.
Of much importance is the concept t h a t an olefin will attract a
carbonium ion in t h e same sense as i t will attract a proton. There-

INDUSTRIAL AND ENGINEERING CHEMISTRY

November 1949

fore, the initial structure of a polymer ion can be directly p r e

dicted, as first proposed by Whitmore (37). For example, isobutene dimer ion will be:
C
C-Cf I

. 3-

c
c
c-c-c-c-c
I
I

c=c-c
I

--f

ei

tert-Butyl Ion

Isobutene

Iso-Octyl Carbonium Ion

with the Carbonium ion carbon atom in the beta position to the
added positive group.
Carbonium ions undergo several types of rearrangement (56,
38, 99) which will determine the structure of the final product.
These rearrangements are in general accord with the relative
energies of the initial and rearranged ions as specified directly
by, or by analogy with, the Evans and Polanyi values, but there
are not yet adequate data to cover all cases.
Two of the most important rearrangements comprise a shift of
hydrogen or a methyl group, which are best explained as movement of a proton or methyl carbonium ion, respectively. This
provides a pattern more consistent with the energetics of the
system than does the H - or CHa- shift proposed by Whitmore
(36). These reactions are shown as follows:

H
H,+--cH,

S H

+Hzc=LCH,
H+

H
Primary Ion

Olefin

NoC-+--CH8

--f

+ Proton

(1)

Secondary Ion

in which n-propyl ion becomes sec-propyl ion via movement of a

proton through ah intermediate resonance position (36).

H~c-cH-cH~-~-cH,

-+HaC-CH=CH$

i.

-ic

CHs

H
I +

H~C-C-CH,
I

as in

Eauation 1

H~C---~~--CH~ (2)
I

Here the sec-butyl ion becomes the more stable tertbutyl ion by
skeletal isomerization via movement of a methyl carbonium ion.
It is the key step in the important secondary reaction of olefin
skeletal isomerization ($4). These rearrangements will be seen
later to have much influence upon the minimum size of the fragments produced in catalytic cracking.
Finally, an ole& nil1 accept a proton In a definite position,
yielding a specific carbonium ion. This ion, either directly or
after rearrangement, may dissociate to a smaller olefin and a
carbonium ion. The latter can then dissociate to a proton and
an olefin. This is the essence of the catalytic cracking of olefins, and is the mechanism of depolymerization of olefins (by acid
catalysts) for the special case of the cracked product being identical with the monomer.
In conclusion, the high reactivity of olefins in catalytic cracking
and other acid-catalyzed systems may be ascribed t o the high
attraction of the ethylenic double bond for a proton, which results
in the rapid formation of reactive carbonium ions.
Saturates (Paraffins and Naphthenes): The catalytic cracking
of petroleum saturates-namely, paraffins and naphthenesposes a special problem. There are no Pi, or double bond, electrons available for direct proton attack as in olefins, nor are the
hydrogen atoms rapidly exchanged for protons (or their isotopes)
in dilute acids, as are those in aromatics (17). Since cetane

2579

cracks in a manner similiar to cetene but much more slowly, it is

logical to postulate the dow formation of a carbonium ion from
cetane as the first step to establish a common point of departure
for their subsequent reactions.
Therefore, a mode of initial formation of carbonium ions from
saturates is required To avoid the step of removing a hydride
ion therefrom directly by the catalyst to give a carbonium ion,
Thomas (8.2)proposed that saturates first undergo some thermal
cracking to give olefins, which then become carbonium ions by
simple proton addition. After cracking, the small carbonium
ions produced continue the reaction chainwise via the hydride
ion exchange mechanism proposed by Bartlett (1) for the alkylation of olefins with paraffins.
This reaction may be written, for example, as
tert-CaHp+

+ iso-C6HIZ--+ iso-CaHlo + tert-CaH1,+

in which a hydride ion (H- or H:) is transferred from isopentane

to the tertbutyl ion, yielding tert-amyl ion and isobutane.
The same problem of the initiatory mechanism arises in the
carbonium ion reaction of butane isomerization, which has been
reported to occur in the absence of olefins or other promoters
using HBr 3. AIBrs catalyst ($1, page 825, Table IV). Other
evidence (3.4) indicates need of a promoting agent; even 0.01%
butenes suffice. There are many additional data bearing on this
quastion, including the effects of hydrogen, oxygen, and mater
@I), which lead to the conclusion that it is difficult to decide
which of the several following possibilities initiates the attack of
the acid catalyst upon butane: ( a ) direct attack of catalyst proton to remove hydride ion from paraffin, yielding molecular
hydrogen (5); ( b ) addition of catalyst proton to traces of olefin
to start paraffi-carbonium ion exchange; ( c ) dehydrogenation of
p a r a f i by oxygen to yield olefin to react as in ( b ) ; ( d ) addition of
catalyst proton to water to provide hydronium ion (H30+)which
may attack paraffin as in ( a ) ; (e) formation of catalyst-promoter
complex which provides a sufficiently activated proton to react
as in (a).
All these possibilities enter into the catalytic cracking of saturates, except that ( b ) may corraspond to olefinsderived from some
thermal cracking and (e) becomes even more indefinite.
Aromatics: The catalytic cracking of aromatics differs greatly
from that of paraffins, olefins, and naphthenes. It is discussed
separately at the end of the text.
Cracking qf Cetane over an Acidic Oxide Type Catalyst (UOP-B).
Using the principles set forth, the results of cracking cetane will
be discussed in detail. Secondary reactions of olefins (34) play
an important part in determining the composition of the final
products of catalytic cracking, among which reactions those of
doublebond isomerization, skeletal isomerization, and hydrogen
transfer are greatly influenced by experimental conditions. Since
the purpose of this work is to study the primary cracking reactions, all products have been grouped according to carbon
number; thereby the effects of these secondary reactions are
largely removed from view. Table VI11 presents a series of five
new experiments the authors have made with cetane up to a
twenty-five-fold increase of flow rate; other conditions were
constant, and the percentage cracked varied from 11 to 68%.
Excellent consistency of product distribution by carbon number
is seen to hold, with only 5% deviation from the average total
361 moles of hydrocarbon product per 100 moles cetane cracked.
These data indicate that a uniform mechanism of primary cracking prevails in this system, and that it should be possible to apply
definite rules thereto with the aim of predicting product distr?oution.
Reaction Mechanism for the Cracking of Cetane (or Any
Kormal Paraffin): From the data in Table VI11 a mechanism
based on the properties of carbonium ions has been devised to
explain the cracking of cetane, the same in many respects as that
which Thomas (32) proposed, without specific calculation, to
woctme. The steprvise process in a certain formalistic sense

INDUSTRIAL AND ENGINEERING CHEMISTRY

2580

TABLE
VIII. CATALYTIC
CRACKING
OF CETANE
(Temperature, 500 C.; catalyst UOP-B. ressure, atmospheric; process
pdiod, 1hoh7
Run
C-614 C-679 C-578 C-613 C-587
Flow rate moles/l./hr.
85.2 3 4 . 0 13 6
8.8
3.4
Conversidn, w t . % (through Cir) 11.0 24.2 40.0 53.5 68.0

17

87

103
53
35
17
9

7
3
3
2
1
1
343
12

12
97
102

64
60
8

8
3
3
2
2
2

16
112
116
43
38
7
8
7
4

3
1
1
1

12

11

113
116

18
115
113

29

32
7

18

60

SO
5

2
1
1

3
2

1
1
E 361 3% 367
Total hydrocarbon
12
9
12
14
Hydrogen
.
a Cia was not determined in these tcsts. I n some similar experiments
one mole of CISproduct was obtained per 100 moles of cetane cracked.
I

shows parallelism to the R-X mode of thermal cracking. Thus,

hydrogen is first removed from the molecule, leaving a hydrogendeficient entity, which then cracks at a carbon-carbon bond beta
to the hydrogen-deficient carbon atom, producing an alpha ole&
and a new hydrogen-deficient entity. The latter repeats the
process until a small uncrackable group is left, which then becomes saturated by acquisition of hydrogen. However, applied
to this generalized process are the definite, special properties of
carbonium ions. These govern the primary cracking reactions
by the preferential formation of certain initial carbonium ions,
the rearrangement of most primary to secondary ions, and some
secondary to tertiary ions, and the cracking of these ions into
fragments not smaller than three carbon atoms each. These
properties also govern many of the secondary reactions by the
almost complete equilibrat,ion of olefin double bonds, the extensive skeletal isonierization of olefins, and the saturation of olefins by hydrogen transfer. The product distribution d t h respect to carbon number, paraffin to olefin ratio, and paraffin and
olefin isomers is thereby greatly altered from that of thermal
cracking, and in a very characteristic and definable manner.
The differences in energy of the isomeric forms of a given carbonium ion are determinative features of cracking over acid oatalysts, because most of the carbonium ion reactions dealt with
here, with the exception of hydrogen transfer, include the isomerization of carbonium ions (both hydrogen shift and skeletal
rearrangement) as an essential step. Their energies decrease
and their stabilities increase in the order primary, secondary,
tertiary. Accordingly the following mechanism of cetane cracking is set forth:
STAGEI. The cetane molecule first reacts with a proton or
small carbonium ion at the surface of the catalyst to form cetyl
carbonium ion by the loss of a hydride ion, H-. Secondary
cetyl carbonium ions will immediately predominate, since there
are twenty-eight secondary and only six primary hydrogen atoms,
and the latter are twice as slow to be removed, as will be shown
later. Furthermore, any primary ions formed may rearrange to
secondary ions before cracking, in accordance with the observed
properties of carbonium ion systems.
H
Example: Cl&

I
+ GHi+ +C6HlI-F-ClOHPI

+ C3Ha

For simplicity, the important rearrangement of Becondsry to

tertiary carbonium ions has been omitted in this description.
The significance of carbonium ion rearrangement, with respect
to product distribution is this: Secondary ions can give no olefins
smaller than Cs, since a secondary carbonium ion carbon atom
by definition must be at least in the 2 position with respect to the
end of the chain. Beta fission ail1 then yield propylene as the
smallest product olefin. Since a tertiary carbonium ion is more
stable than a secondary carbonium ion, a number of secondary
ions will rearmnge to tertiary, still leaving the carbonium ion

Vol. 41, No, 11

carbon atom in at least the 2 position with respect to the end of

the chain. Beta fission in this case will yield isobutylene as the
smallest product olefin. Therefore, the smallest fragments in
important yield from catalytic cracking are Ca and C, hydrocarbons, Any large olefins initially formed will tend to recrack because of their great reactivity over acidic oxide catalysts. Finally,
the theory .and data indicate that carbonium ions that cannot
crack by this mechanism into two fragments, eachCaor larger, will
crack but very little, which corresponds to the large amounts of
Cg and iso-C6 in the product. Of course, some methane and CZ
are formed, which need not be ascribed to thermal cracking, but
to adequate activation of much less favored types of cracking.
Convincing evidence of this rearrangement is found in cetane
cracking, which gives large amounts of small isoparaffins. Thw,
at 11% conversion, 99 moles of total paraffins came from 100
moles cetane cracked (in nearly complete hydrogen balance), of
which 53 moles were isoparaffins. Since 30 moles were CHI, CzHe,
and CsHs, the significant is0 to normal ratio is then 53 to 16.
STAGE11. The carbonium ion will split at a carbon-carbon
bond in a beta position to the carbonium ion carbon atom. The
two electrons from this bond will move to the original carbonium
ion carbon atom and neutralize the single positive charge, simultaneously forming an ethylenic double bond. Thus, an alpha
olefin is produced which rearranges, and the other fragment
becomes a primary carbonium ion, Example:

STAGE111. The primary carbonium ion derived from cracking

will in turn rearzange to a secondary carbonium ion a3 in stage I
and crack beta to the carbonium ion carbon atom as before.

Example: H J - C ~ H I ~+HaC--C-GHls
-r
H
HIC-C=CHZ

--+
-i-H&-CSHii
+

This process will continue until a carbonium ion which cannot

yield fragments of three or more carbon atoms is producedfor example, a normal secondary CS carbonium ion. It is ar
experimental fact that methyl and ethyl carbonium ions are harc
to produce; this corresponds to their high electron impac
appearance potentials (16) from their parent paraffins. There
fore, cracking to such small ions occurs to but a small extent.
STAGE
I f . The final carbonium ion from stage 111reacts wit
a new cetane molecule by hydride ion exchange to produce a sma
paraffin and a new cetyl carbonium ion, thereby propagating tE
reaction chain. The example is the same as in stage I.
The beta fission rule is not a purely arbitrary law, but is
description of that mode of molecular division which will yield
neutral olefin and ti smaller carbonium ion without the rearrang
ment of any carbon or hydrogen atoms within the ion during t
cracking process. Only electrons are shifted, and then only frc
one side to the other of the prospective ethylenic carbon atom
the point of division. This mode of behavior corresponds to I
principle of least motion or the principle of least rearrangeme
It has been shown in the analogous case of free radicals that SI
a process should have a lower work of activation than any ot
possible process (2, 87).
To illustrate the applicability of these rules to cetane,
experimental and calculated product distributions by car
number are shown in Table I and Figure 1. Calculations v
made on the following basis:
1. Cetane forms cetyl carbonium ion by random loss of
dride ion from any secondary position.
2. The secondary cetyl carbonium ion cracks at a bond
to the carbonium ion carbon, forming an olefin, CnH2, a
primary carbonium ion, CI~--nH+33-z,1.(Whenever altern
bonds are available ior cracking, all are considered equally,
viding that fragments Ca or larger are formed.) The pri
carbonium ion then isomerizes by proton shift to an equa
tribution of all possible secondary ions. Continued crackin
isomerization proceeds w described until all ions are reduc
c
6 or smaller. These become amall parafins by acquir
hydride ion.
3. The olefins formed in step 2 should react about j
extent to be expected from the authors cracking tests wit
olefin feeds. Accordingly, half of these olefins are assur
form carbonium ions which then crack according to thr
outlined above. The extent of recracking of olefins wi!
with the experimental conditions.

INDUSTRIAL AND ENGINEERING CHEMISTRY

November 1949

'

--- ---- -_----

lo
CARBON No. EOF PRODUCT

Figure 1.

I'

l2

l3

l4

l5

Catalytic Cracking of Cetane at 500' C. .

Experimental, 24% conversion over UOP-B catalyst

Cracking of the Five Hexane Isomers over UOP-B Catalyst.

These experiments on the cracking of the five hexane isomers over
activated carbon provided data for the calculation of the relative
reactivities of primary ( P ) , secondary (S), and tertiary ( T )
hydrogen. A similar calculation may be made for UOP-B
catalyst a t 550" C. using the authors' data (9),as will be shown,
leading to the coefficients P = 0.62, S = 1.29, and T = 12.3%
of charge. These coefficients, when multiplied by the number of
C-H bonds of corresponding type, add up to the extent of cracking
of a given hexane isomer.
Hexane Isomer
2 3-Dimethylbutane
;-Hexane
2,2-Dimethylbutitne

Number and Type of

C-H Bonds
12P
2T
OP
8s

+
+
12P + 2s

% Cracked
32
14
10

The relative values for the three types of C-H bonds are then close
to 1, 2, and 20 for P, S, and T a t 550" C. For comparison, the
R K thermal values a t 500" C. were 1.0,3.66, and 13.4, and those
calculated for activated carbon were 1.0, 3.66, and 11.0, respectively.
These data lead to the conclusion that the relative rates of
removal of hydride ions fall in the same order as those for the
removal of hydrogen atoms, but the values are different. Of
particular significance is the high value for tertiary hydrogen for
cracking with an acidic oxide catalyst.
Applying these numbers to the cracking of the two other hexane
isomers, good agreement is obtained, as shown in Table IX.
I n addition, the cracking of two octanes and two dodecanes is
shown, with good agreement of relative rates. The effect of
molecular weight on extent of cracking is not simple (9, 10, 1.9)
and has been left out of consideration.
As in the case of activated carbon, the determinative influence
of the numbers and types of carbon-hydrogen bonds on the extent
of cracking provides strong indication that the carbon-hydrogen
bond is the critical point of attack in paraffins. The experiments

TABLEIX.

CATALYTIC
CRACKING
OF HYDROCARBONS
AT
550' C. OVER UOP-BCATALYST

Conversion, Wt. % of
Numbers and
Total Products
Types of C-H
Hydrocarbon
Experimental Calculateda
Bond Present
(a) 2-Methylpentans
25
23
9 P 4 5 1T
(b) 3-Methylpentane,
25
23
9P: 4s: 1T
ratio a/b
1.0
1.0
( a ) Isooctane
49
24
16P, 2S, IT
(b) n - O o t a n ~ ,
42
19
0 P , 12s
ratio a / b
1.2
1.3
(a) n-Dodecane
35
30
6P 2 0 s
(b) Isododecane,
32
31
21P:4S, 1T
ratio a / b
1.1
1.0
a Feed space rates were not the same for the digerent groups of isomers
and other factors enter into the differences between the ex erimental and
calculated absolute conversions of Cs and CIZ such as the e&ct of molecular weight, so t h a t only the ratios a / b are ekpected to agree.

2581

of Hansford (14) which show easier exchange of tertiary hydrogen

(compared with secondary or primary) with deuterium incorporated in a silica-alumina cracking catalyst are in agreement with
this view.
Cracking of Other Hydrocarbon Classes. Naphthenes: The
primary cracking reactions of naphthenes are expected to follow a
pattern similar t o that of paraffins (IS,32). Naphthenes have
been thought to be more reactive than paraffinsof a similar molecular weight ( I S ) . However, certain naphthenes and parafKns
with the same number of carbon atoms and about the same number and types of carbon-hydrogen groupings more recently have
been found by the authors to crack at similar rates (9). Thus,
Decalin and 2,7-dimethyloctane (CIO hydrocarbons with two
tertiary carbon atoms) showed similar conversions (runs C-641
and 642 in Table X). These results indicate that the naphthene
ring structure by itself may be of secondary importance in determining the rate of cracking over this acidic oxide catalyst.
Olefins: In accordance with the prior discussions of olefin and
paraffi reactions, the formation of a carbonium ion is postulated
to be the first step in their cracking. The very rapid addition
reactions of proton to olefin (or of a small carbonium ion to an
olefin to give a larger carbonium ion) account for the high response of olefins to acid catalysts. The Carbonium ion is the common intermediate in both paraffin and olefin cracking; according
to the mechanism of para& cracking set forth earlier in the
text, the cracked products should in general be similar for paraffins and olefins of similar skeletal structure, differing mainly in
degree of saturation and extent of recracking of product olefins
(11). This is shown in run C-46, Table XI.
Several secondary reactions of olefins, which contribute to the
ultimate product distribution in catalytic cracking, have already
been discussed. One other important secondary reaction, that of
hydrogen transfer, as exemplified by the saturation of olefins,
proceeds by two steps, the addition of a proton to olefin to form
a carbonium ion, and the transfer of hydride ion from a neutral
donor molecule to give a saturate and a new carbonium ion
derived from the donor. Thus,
(CHa)&=CH2

or, (CH3)sC+

+ H + + (CHa)aC*

+ (CH&C=CH1

--+

(CH&CH

+ C&+

The donor may then lose a proton to become a 185s saturated

molecule. This reaction is another example of hydride ion exchange, as proposed by Bartlett (1, page 1536). An identical
mechanism waa proposed by Thomas (Sf?).
Tertiary carbonium ions are formed more readily (6) than secondary ions, and this difference is believed t o be related to the
preferential saturation of tertiary olefins in catalytic cracking
(34).
Aromatics: Alkyl-substituted aromatic hydrocarbons are
highly reactive in catalytic cracking systems when the alkyl
groups are Ca or larger. Therefore, the characteristics of both
the aromatic ring and the alkyl side chain are responsible for the
ease of cracking of such compounds, although the aromatic nucleus remains essentially intact. The unique properties of the
benzene ring with respect to protons are now reviewed in the
light of well-known concepts. First, there is much unsaturation
in the benzene ring, but there are no ethylenic double bonds,
since the six surplus (Pi) electrons are resonating among all the
carbon-to-carbon bonds. Therefore, n6 simple ethylenic double
bond type of carbonium ion can be formed without altering the
resonance energy of the benzene ring. Secondly, the benzene
ring has much affinity for protons in the sense of attracting them
and exchanging the hydrogen (or deuterium) originally present

INDUSTRIAL AND ENGINEERING CHEMISTRY

2582

3g 2 c o -1m09

B 6%"

.. .. .. .. .. .. .. .. ..
. . . . . . . . .

for protons (or deuterons) in the vicinity,

demonstrated by Ingold and co-workers
( 1 7 ) with sulfuric acid a s cat,alyst. Thus,

.. .. .. .. .. .. .. .. . . . . s
".N.??R
mm-ocy
. . . . . . . . .
0,

Vol. 41, No. 11

ati

.. .. .. . . . . . .. .. .. .. .. . . . . . . .ca:u?*'Ludi
.o .t -.i c.'y*
. . . . . . . . . . . . . . Ncld
0

+ 1.'H
where a n intermediate form is depicted to
indicate the hypothetical transition state.
The authors believe that the same
mechanism can be applied t o the alkylation of aromatics, by assuming t h a t a n
alkyl carbonium ion plays the same part as
a proton, as follows:

where R +is a n alkyl carbonium ion derived

from the combination of an olefin and a
proton. The cracking of aromatics over
acidic catalysts is t h e exact reverse of this
reaction, followed by the dissociation of R +
t o a n olefin and a proton. Thus

ii

.C

L
R

The distinctive characteristic of catalytic

compared with thermal cracking of alkyl
aromatics is the severance of the entire alkyl
group from the ring, instead of cracking of
a carbon-to-carbon bond within the side
chain. This has been extensively reported
(IS), and i t is plain t h a t t h e rates of cracking of isomeric alkyl aromatics correspond
t o t h e relative ease of formation of the several carbonium ions. Suitable data are
not available for computing the strength of
attachment of a n alkyl carbonium ion t o an
aromatic ring for comparison with the same
covalent bond strength. However, the
energies of combination of methyl, ethyl,
isopropyl, and tertiary butyl positive ions
with hydride ion (H-) are 319, 282, 264,
and 247 kg.-cal., respectively (26, 69). The
energy differences in this series are similar
when a n alkyl group is substituted for hydrogen and may be assumed t o be correspondingly similar with respect t o a n aromatic
nucleus. These differences may be correlated with the relative extents of cracking
(dealkylation) of methyl-, ethyl-, and isopropylbenzenes, which are 1, 11, and 8470,
respectively, at 500" C. under the same ex-

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTR,Y

November 1949

Hydrocarbon
Catalyst
Temperature, C:
Process period, min.
Liquid. hourly space
velocity
Conversion wt. %
'
Moles product/100
moles cracked
HZ
CHI
Cz H4

CzHa

CUHS

Ca He
C4Ha
dSO-CIH8
n-C&
iso-C4Hio
n-CIHio
tert-CsHio
sec-CsHlo
i80-CsHit
n-CsHiz
Ce (74O)d
c7 (990)
C8 (125')
Ce (152O)
Cio (174')

2;t%,'

Cia ( 2 3 8 9
(255')
Cia 273')
ClS t2900)
ci4

Total
Material balance, wt.
% of charge
Gas below Ca
Liquid boiling below
feed
Remainingliquid
Coke on catalyst

Loss

Run

TABLE
XI. DATAON

THE CRACKING
OF PUREHYDROCARBONS
Cetane
7-CeteneWax
-CarbonSilica Quartz" Alumina UOP-B -Carbon500
400
500
550
270
6
-090

UOP-B
60

-.

24.5
11.0

10.0
24.2

4.0
40.0

2.0
53.5

1.0
68.0

10.0
26.6

3.9
68.4

0.5
20.9

0.05
31.5

12

12
5
7
5
76
21
0
26
39
25
12
25
17
16
6
50
8
8
3
3
2
2
2

14
4
9
7
85
27
1
28
40
32
15
14
10
13
6
38
7
8
7
4

9
12
10

12
11
9
9
81
34
1
20
31
44
17
16

26
11

16
13

33

17
53
77
53
47

11
6
68
19
0
29
41
22
11
23
14
11
5
35
17
9
7
3
3
2

......
......

355370
4.9
5.8
89.4
0.3
-0.4
C-614

82
31
0
25
37
37
17
21
13
20
6
29
9
5
4
3
3
2
1

3
1
1
1

...
...

375

...

16
9
14
0
0
6
0
11
1

...
...

11
21
15
9
18
15
14
13
7
4
14

35

19
10
18

58
46
40
17

1
23
1
4
3
14

0
1
8

15
2

10

19
5
32
7
5
5
4
3
2
1
1

8
1

17
16
24
13
20
16
10
14
7
4
4

2
18
14

15

10
7
10
7
5

... - ... ... ...

385
379
249
263
373

13

2
2
16
1
2
3
6
0
0
24
16
13
10
11
9
7
8

...
...

395

0.5
61.7
199
29
24
20
42
16
0
17
26

3
7

Thermal run.
Carbon only.
Negative values si nify gain.
1 Upper cut points for Cn fractions from aliphatic feedstocks in
epectively.
C

' C.

15
18

15
3
4

15

7.9
37.8

31.7
44.0

13
21
7
20
17
16
0
0
10
0
13
1

15
25
31
29
27
19

1
14
1
12

8
1

42

7
23
10
16
17
10
12
11
10
7

73

7--CumeneUOP-B Carbon Alumina

-500r
60
-1.983.6

7.5

73
62
12
11

3
1
1

78
1
0
1

52
0
0

:}

6
0

0
0
0

100

29
24
20
19
20
15
17
14
11
12
7
378

11.1

13
20
25

...
...
...
...

....
..
...
...
...

...

...
...
...
... ... ... - ...
is- 282. . .
239
495
259

37.1
38.1
3.9
0.4
C-931

10.8

10

19.2
69.3
0.7
-1.1
C-590

3.3

1
16

12.8
17.7
23.4
29.2
22.7
57.1
12.7
75.3
59.4
45.9
31.9
72.6
31.3
78.9
0.1
1.1
1.1
2.3
0.3
0.0
0.9
0.7
1 0
1.2
0.1
1.1
0.8
0.2
C-579 C-578 C-613 C-587 '2-708 (2-710 C-930

36.5

33

20.5

28.4

1
3

10
1
5
11
15
11
12
11

11.9

20.8

2.0
62.0

7.3

11.1

2583

8.4

6.2

7.5

49.4
28.7
35.8
36 2
61.2
55.6
1:2b 2.2
0.4
4.8
1.7
0.7
'2-46 C-721 C-715

...

23.3
50.7
15 3
3:9*
6.8
C-131

2.9

3.9

3.3
6.7
90.2
88.3
1.1
0.4
2.5
0.7
'2-686 C-1015

The CS,CT, and Cs fractions from cumene were cut a t 99O, 125' and 150' C., re-

perimental conditions (13). Normal, secondary, and tertiary

butyibenzenes cracked 14, 52, and 84%, respectively, a t only
400" C. (IS). The relation of the ease of cracking t o the differences in energy of the carbonium ions is clearly apparent and
provides support for the belief t h a t the reaction corresponds t o
the carbonium ion mechanism.
Further information can be obtained by changing the electron distribution in the benzene ring. Thus, in an enlightening
study by Roberts (88) of these laboratories on the cracking of
cumenes substituted in particular manners, their cracking rates
decreased in the order: 1,3-dimethy1-Pisopropylbenzene>pcymene > 1,3-dimethy1-5-isopropylbenzene > cumene > p
chlorocumene > trichlorocumene, which corresponds t o the
order of decreasing electron density of the carbon atom bonded
to the isopropyl group (89). This is added evidence for the
proposed cracking mechanism-namely, proton attack a t the
ring carbon atom which carries the vulnerable isopropyl group.
ACKNOWLEDGMENT

The pioneer work of F. C. Whitmore on carbonium ion systems

has provided basic concepts for the mechanism of reactions of
hydrocarbons in the presence of acidic catalysts. The work of
P. D. Bartlett ( I ) on the role of hydride ion in alkylation has
supplied an essential step t o explain the cracking of saturates
and the transfer of hydrogen t o olefins.
The authors acknowledge appreciatively the earlier unpublished
work (38) of Charles L. Thomas, then of Universal Oil Products
Company, upon an independent approach t o the problem in
terms of carbonium ion theory and the intrinsic acidity of the
catalysts employed. The work of F. 0. Rice and A. Kossiakoff on
free radical cracking mechanisms has been applied with success t o
the thermal cracking of relatively large paraffins and has proved
t o be of much use in comparing different cracking systems.
The authors particularly thank A. E. LacomblO, chairman
of the board of directors and former director of research, for his

interest and encouragement, The data and information supplied by the work of their colleagues, 0. Beeck, M. W.Tamele,
R.C. Archibald, R . M. Roberts, D. P. Stevenson, C. W. Bittner,
C. P. Brewer, J. W. Gibson, N. C . May, and D . H. Rowe, as well
as their helpful suggestions, are most appreciatively acknowledged.
CATALYSTS

ALUMINA
(low silica). From aluminum chloride by precipitation with ammonium hydroxide followed by washing. Dried
at 150" C., calcined a t 565' C. F e 0.001-0.01%, Si 0.03-0.010/0,
and traces of Cu, Mg, Mo, Sn, Ag, Ni, Ca, and Cr by spectrographic analysis. Loss on ignition a t 1000" C., 33.3% by weight.
Specific surface 180 m.a/g.
ACTIVATEDCARBON. Columbia Activated Carbon, Grade
S,size 4-14, A2, mesh, Carbide and Carbon Chemicals Corporation. Calcined at 565" C. Specific surface 1600 m.a/g. Ash
content, 2.1%.
SILICA(low alumina). Made by Shell Development Compan
Wilmington, Calif. AI less than O.OOl%, Ca 0.02%. Spec&
surface 531 m.e/g. Bulk density 0.38.
SILICA-ZIRCONIA-ALUMINA.
Universal Oil Products Company, Type B, l/a-inch pills. Three lots were used:
1. UOP-B. This lot waa used for all runs except for those
listed later. Specific surface 346 m.e/g.
2. UOP-B-2 used in run C-46.
3. .UOP-B (R-51) used in runs C-139 and 140. Contained
86.2% silica, 9.4% zirconia, and 4.3% alumina.
FEEDSTOCKS

Feedstocks are arranged in order of carbon number.

TL-HEXANE.
Stock A. Shell Oil Company Inc., Houston, Tex. Boiling
range wss 0.4" C., nv 1.3759, dO
:
0.6613, bromine No. 0.2.
Used in run C-623.
Stock B. Phillips Petroleum Company. n?
1.3753,
dO
: 0.6611, bromine No. 0.2. Used in run C-822.
Z-METHYLPENTANE.
Stock A. From hydrogenation of 2-methylpentenes. Boiling range 59.6-66.0" C., n v 1.3730, d i 0 0.6603, bromine No.
0.3. Used in run C-529.
Stock B. Phillips Petroleum Company. Technical grade,
designated greater than 95% pure. Used in run (2-996.

INDUSTRIAL AND ENGINEERING CHEMISTRY

2584

3-METHYLPENTANE.
Stock A. Distilled from hydrogenated catalytically cracked
gasoline from Standard Oil Company of New Jersey (Louisiana
division). After silica gel treatment, boiling range was 0.4" C.,
a? 1.3755, dzo 0.6619, bromine No. 0.2. Used in runs '2-530
and 553.
Stock B. Phillips Petroleum Company.
1.3772,
dqo 0.6638, bromine No. 0.5. Used in runs C-821 and 998.
2,3-DIhlETHYLBUT.4KE. From alkylation of isobutane with
ethylene. Boiling range 56.5-57.3' C., ny 1.3732, d:" 0.6603,
bromine KO. 0.3.
NEOHEXANE.
Stock A. From isomerization of methylpentanes with AlCla
catalyst. Boiling range 48.5-48.9" C., nZ,O 1.3710, d i 0 0.6542,
bromine No. 0.3. Used in run C-527.
Stock B. Phillips Petroleum Company. n2$ 1.3690,
d?" 0.6492. bromine h'o. 0.01. TJsed in run '2-823.
OCTANE. Eastman 1Codal< Company. Roiling range 124126.2" C., nag 1.3978, d i 0 3.7025, bromine No. 0.16.
ISOOCTANE.
Shell Oil Company, Inc. Boiling- range
- 98.699.4" C., n%?1.3925, d ? O 0.6935; bromine KO.0.04.
CUMENE.
Stock A. Dow Chemical Company. Boiling range 152153" C., n y 1.4912, dZo 0.8621. Used in run C-131.
Stock B. Eastman Kodak Company. n9 1.4908, d:"
0.8629. Used in run C-1015 (97.7y0 cumene by infrared analysis).
Stock C. From alkylation of benzene with propylene.
0.8579,
Boiling range, 95% from 150-152.7" C., n2,0 1.4886,
bromine KO.3.3. Used in run C-686.
DECALIN.Eastman Kodak Company. Purified over silica
gel. n? 1.4755, dO
: 0.8837, bromine No. 0.4.
2,7-DIMETHYLOCTANE. Eastman Kodak Company. Boiling
range 158-160" C., ny 1.4089, d i 0 0.7248, bromine No. 2.4.
~-DODECANE.
From lauryl alcohol from Eastman Kodak
Company. Boiling point 217" C., melting point -9.8" C.,
nSo 1.4216, dO
: 0.7486.
ISODODECANE.
Hydrogenated triisobutenes from Shell Oil
Company, Inc. from cold acid polymerization of isobutene.
A.S.T.M. 5% and 95y0 distillation temperatures were 175.8' and
178.7"C., n2$ 1.4201, dO
: 0.7474, bromine No. 3.9.
CETENE. N. V. de Bataafsche Pet,roleum Mij., Delft, Holland.
Stock A. Melting point 4.05" C., n'g 1.4409, d i o 0.7813,
bromine KO.69.3. Used in run C-46.
Stock B. Melting point 3.6" C., n y 1.4398, dqo 0.7822,
bromine No. 68.5. Used in run C-721.
CETANE. E. I. du Pont de Nemours & Company, Inc. Several
lots of similar properties were used. Range of properties: melting point _16.7-17.0" C., ng 1.4345-1.4348, d i 0 0.7726-0.7742,
bromine no. 0.2-0.3.
BORNEO
Wax. Kestern Waxed Paper Company, Emeryville,
Calif. nY 1.4356, d:" 0.7786, melting point 53.4" C., molecular weight 368.

Brunauer, S., Emmett, P. H., and Teller, E., Z b i d . , 60, 309

(1938).
Dobryanskii, A . F., Kanep, E. K., and Katsman, S. V., Trans.
Reaearch Plant Khimgaz, 3, 1 (1936).
Evans, A . G., and Polanyi, M., J . Chem. Soc., 1947, p. 252.
Frost, A . V., J . Phgs. Chem. (U.S.S.R.), 14, N o . 9/10, 1313-18
(1940).
Gault, H., and Altchidjian, Y., Ann. chim., (10) 2, 209 (1924).
Good, G. M . , Voge, H. H., and Greensfelder, B. S.,IND.ENG.
CHEM.,
39, 1032 (1947).
Greensfelder, B. S.,
and Voge, H. H., Ibid., 37, 514 (1945).
Ibid., p. 983.
Ibid., p. 1038.
Greensfelder, B. S., Voge, H . H., and Good, G. M . , I h i d . ,
p. 1168.
Hansford, R. C., Ibid., 39, 849 (1947).
Henriques, H. J., Ibid., p, 1564.
Hipple, J. A . , and Stevenson, D. P., J . Am. Chem. SOC.,64,
1590, 2766, 2769 (1942).
Ingold, C. K., Raisin, C. G., and Wilson, C. L., Nature, 134,
847 (1934) ; J . Chem. Soc., 1936, pp. 915, 1643.
Kasanskii. B. A., and Plate, A . F., Ber., 67, 1023 (1934).
Kossiakoff, A , and Rice, F. O., J . Am. Chem. SOC.,65, 590
(1943).
Marisic, M. M. (to Socony-Vacuum Oil C o . ) ,U. S.Patent 2,394,796 (1946).
Oblad, A. G., and Gorin, hf. H., ISD. ESG. CHEM.,38, 822
(1946).
Pauling, Linus, "The Nat,ure of the Chemical Bond," 2nd ed.,
Ithaca, N. Y . ,Cornell University Press, 1940.
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nso

LITERATURE CITED

(1) Bartlett, P. D., Condon, F. E., and SchneideI, A , J. Am. Chem.

Soc., 66, 1531 (1944).
( 2 ) Bawn, C . E. H., Trans. Faraday Soc., 34, 598 (1938).
(3) Bloch, H. S., Pines, H., and Schmerling, L., J . Am. Chem. Soc.,

68, 153 (1946).

Vapor pressure
of Maleic

Vol. 41, No. 11

(1946).

Rice, F. O., Ibid., 55, 3035 (1933).

Rice, F. O., and Rice, K. K., "The Aliphatic Free Radicals,"
Baltimore, Johns Hopkins Press, 1938.
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Thomas, C. L., IND.ENQ.CHEM.,41, 2564 (1949).
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(1949).
Voge, H. H., Good, G. AM.,and Greensfelder, B. S., IND.ENG.
CHEM.,38, 1033 (1946)
Wheland, G. W., "The Theory of Resonance," pp. 233--4,
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Whitmore, F. C., Chem. knp. News,26, 668 (1948).
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Whitmore, F. C . , and Stahly, E. E., Ibid., 55, 4153 (1933).
I

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RECEIYED
August 2 , 1948.

LEON 0. WINSTROM AND LAURENCE KULP'

Allied Chemical and Dye Corporation, New York, N . y .

TEMPERATURE RANGE
FROM 35" TO 77" C.

T h e vapor pressure of maleic anhydride has been

measured in the temperature range from 35" to 77" C.
A new static method for the measurement of the vapor
pressure of sublimable substances is described.

URIKG the course of process development in expanding

the production of maleic anhydride (Toxilic anhydride),
it became necessary t o know the vapor pressure of this substance
a t temperatures near its melting point. The only data available
in the literature are those tabulated in Landolt-Bornstein (4)
which refer t o unpublished data obtained from I. G. Farben.
Weiss and Down8 (6) determined this property a t higher teniperatures but they give only one value in the range of interest,.
1

Present address, Coliimbia University, New York 27, S . Y .