KINETICB OF ETHYLENE

AND MECHANISM OXIDATION 1493

Kinetics and Mechanism of Ethylene Oxidation. Reactions of

Ethylene and Ethylene Oxide on a Silver Catalyst

by Robert E. Kenson' and M. Lapkin2

Chemicals Group Research Laboratory, Olin Corporation, New Haven, Connecticut 06604 (Received June 0, 1069)

The kinetics of the reactions of ethylene and ethylene oxide on a supported silver catalyst were investigated.
The principal reaction of ethylene oxide on silver between 200 and 285' was isomerization to acetaldehyde,
which underwent rapid oxidation to carbon dioxide and water when oxygen was present. The rate law was
determined to be
-dCnHkO/dt = 3 . 9 X lod4(CzH40)1.0
at 200', while E, and A#* were 9.8 =k 0.6 kcal/mol and -55 f 2 eu, respectively. The results were inter-
preted in terms of chemisorption of ethylene oxide as the rate-determining step of the isomerization reaction.
Ethylene was oxidized by the same catalyst in a flow system to ethylene oxide or carbon dioxide and water. The
activation energy of carbon dioxide formation was 7.6 f 15 kcal higher than that of ethylene oxide formation,
which correlates with the difference in stability of atomic and molecular oxygen complexes, respectively, on the
silver catalysts. The mechanism of ethylene oxidation is believed to involve formation of ethylene oxide by
reaction with molecular oxygen, and formation of carbon dioxide and water by reaction with atomic oxygen.

Introduction results of Orzechowski and RiIacCormack,6 who oxidized

The reactions of ethylene oxide over a silver catalyst
were first investigated by T ~ j g g . ~His
. ~discovery that
ethylene oxide was isomerized to acetaldehyde a t
temperatures comparable with those used for the silver-
catalyzed oxidation of ethylene oxide led to further
interest in this reaction,6-7 the purposes of which were to
determine the significance of ethylene oxide isomeriza-
tion in the formation of carbon dioxide. The Twigg
reaction scheme postulates three routes for the oxidation
of ethylene. These \iTere
+ Ag Catalyst
____+ 2CO* +
0 Newark, N. J. 07105.
ethylene oxide in a flow reactor, and Margolis and
RoginsliilB who oxidized C-14 labeled ethylene and
unlabeled ethylene oxide, supported the original con-
clusion that reaction 3 was too slow to account for most
of the carbon dioxide formed. The possibility existed,
however, as conceded by Orzechowski and Mac-
Cormack, that reaction 3 was really part of reaction 2
and that ethylene oxide adsorbed on the catalyst, after
its formation, could be further oxidized to carbon di-
oxide. Recently, however, Ide7 and coworkers, con-
cluded that acetaldehyde was the intermediate by
which ethylene was oxidized to carbon dioxide. With
the exception of Ide, all investigators have made an
important assumption about the physical state of the
ethylene oxide which is isomerized. There is no ques-
(1) Research and Development Department, Engelhard Industries,
(2) To whom all correspondence should be addressed. Olin Corpora-

-
CH,CHO + 5/202 2C02 f 2H2O
This generalized oxidation reaction scheme has been
explicitly or implicitly accepted by most investiga-
t o r ~ ~ of
- ' these
~ reactions. The microscopic details of
the mechanism are steeped in controversies concerning
the relative importance of reaction 3 and the involve-
ment of different adsorbed oxygen species in reactions 1
and 2 , which have decidedly different activation
energies.3 , 4
Twjgg concluded that reaction 3 was a minor source
of carbon dioxide in the oxidation of ethylene. The
tion, Thompson Plastics, Assonet, Mass. 02702.
(3) G. H. Twigg, Proc. Roy. Soc., A188, 92 (1946).
(4) (4) G. H. Twigg, Trans, Faraday Soc., 42, 284 (1946).
(5) A. Orzechowski and K. E. MacCormack, Can. J. Chem., 32, 388
(1954).
(6) L. Ya. Margolis and S. Z. Roginski, Probl. Kinet. Katal., Akad.
Nauk S S S R 9, 107 (1957).
(7) Y. Ide, T . Takagi, and T. Keii, Nippon Kagaku Zasshi, 86, 1249
(1965).
(8) K. E. Hayes, Can. J . Chem., 38, 2256 (1960).
(9) A . I. Kurilenko, N. V. Kul'kova, L. P. Baranova, and M. I.
Tempkin, Kinet. Katal., 3 , 177 (1962).
(10) F. McKim and A. Cambron, Can. J . Res., 27B, 813 (1949).
(11) K. E. Murray, Aust. J . Sci. Res., A3, 2143 (1950).
(12) G. R. Schultse and H. Theile, Erdoel Kohle, 5, 552 (1952).
(13) S.Wan, 2nd. Eng. Chem., 45, 234 (1953).

Volume 74, Number 7 April 8, 1970

 1494
tion that gas-phase ethylene oxide is isomerized slowly
to acetaldehyde within the temperature range used for
ethylene oxidation. Adsorbed ethylene oxide, however,
mould be isomerized more rapidly than gas-phase
ethylene oxide, if the slow step in this process is the
adsorption of the ethylene oxide on the catalyst,14J6
Hence, the isomerization of ethylene oxide to acetalde-
hyde, followed by its oxidation, could be the major
route to carbon dioxide relative to direct oxidation of
ethylene. Therefore, if the rate-determining step in
the isomerization of ethylene oxide to acetaldehyde
could be established, the true importance of reaction 3
in carbon dioxide formation as compared with reaction
2 would be determined. It was decided that an in-
vestigation of the kinetics and thermodynamics of
ethylene oxide isomerization and oxidation over a silver
catalyst be undertaken to resolve this question,
The involvement of oxygen in the oxidation of
ethylene has been an area of disagreement among
various investigators. If reactions 1 and 2 are accepted
as being discrete and separate reactions leading to
ethylene oxide and carbon dioxide, respectively, then i t
is most likely that these reactions involve different
oxygen species adsorbed 011 the silver catalyst. Two
major oxygen species have been discovered on silver
catalysts at temperatures required for ethylene oxida-
tion.16-20 Although disagreement exists as to the
velocity of interconversion of the species as determined
by the use of isotopic o ~ y g e nevidence
, ~ ~ ~ points
~ ~ to one
of these species being molecular (0-0 bonds present)
and the other being atomic (absence of 0-0 bonds).
Attempts t o determine the product obtained from
reaction of ethylene with atomic oxygen produced from
N20 adsorption on silver were made by Schultze and
Theile. l 2 The results were however ambiguous, since
decomposition of N 2 0 on catalytic surfaces leads to
both atomic and molecular oxygen species.21
The adsorption of ethylene on silver is liriown to be
weak3 and therefore could not contribute much to the
known activation energy difference between ethylene
oxide (1) and carbon dioxide formation (2). The
major contribution to this difference ought to be the
relative energy states of the two oxygen species ad-
sorbed on the silver catalyst. It should then be possible
to correlate the difference in activation energies of reac-
tions 1 and 2 and thermodynamics of oxygen adsorp-
tion on silver'6-20 at low surface coverage. Flow
studies of the relative rates of reactions 1 and 2 at
various temperatures were therefore undertaken to
determine the activation energy difference.
Experimental Section
Catalyst. The catalysts utilized for the isomerization
of ethylene oxide and the oxidation of ethylene were ,the
same. They consisted of 0.475 cm X 0.475 cm fused
alumina pellets (Norton SA-101) coated with silver, the
pellets containing 10% by weight silver. The catalyst
The Journal of Physical Chemistry
M, LAPKIN
ROBERTE. KENSON.AND
To Vacuum Pump
Vacuum Test Gauge
Chromatograph
Figure 1. Schematic diagram of reactor for ethylene oxide
isomerization studies in a static system.
was prepared outside this laboratory by reduction at
250" by hydrogen of silver nitrate impregnated onto
the alumina in vacuo at 25". All results were obtained
with the same catalyst batch.
Apparatus. Static System. Figure 1 illustrates the
static reaction apparatus used in the isomerization
studies. It consisted of a feed system and mixing bulb
for the reactants, the reactor, and a vapor phase
chromatograph to analyze the products and reactants.
The reactant feed system consisted of gas-tight 0.635-
cm 0.d. stainless steel tubes and fittings. Needle valves
were used to control gas flows. The gases were pre-
mixed in a stainless steel flask fitted with a Bourdon
tube vacuum test gauge to read the pressures of the
gases. The tubing leading to the reactor from the
mixing bulb was heated by means of a heating tape t o
preheat the gases before they reached the reactor.
The reactor itself consisted of a 3.34-cm 0.d. carbon
steel tube jacketed by a 5.08-cm 0.d. carbon steel tube
containing a heat transfer fluid. This fluid was
circulated through the jacket and to a thermostated
bath by an electric-powered pump. The heat transfer
fluid was a silicone oil which, for the 200" bath, was
now-Corning mold release fluid, and for the higher
temperature runs was General Electric SF-96 silicone
fluid. Teflon-packed toggle valves were used to
isolate the reactor from the preheat section and the
vapor phase chromatograph. The reactor volume of
470 cc was totally filled by 543 g of catalyst.
(14) Physical adsorption, of course, would presumably be rapid and
probably obey a Langmuir-Hinshelwood adsorption isotherm, as
noted by Ide in ref 7. Chemisorption of a molecule on a catalytic
surface can involve an appreciable activation energy and, therefore,
be a rate-determining process.16
(15) B. M. W.Trapnell, "Chemisorption," Academic Press, Inc.,
New York, N.Y.,1955,pp 49-86.
(16) A.W.Czanderna, J . Chem. Phys., 68,2765 (1964).
(17) R. G. Meisenheimer, A . W. Ritchie, D. 0. Schissler, D. I?.
Stevenson, H. H. Voge, and J. N. Wilson, Proc. 2nd. Intern. Consr.
Surface Actiuity, 2, 299 (1957).
(18) Y.L. Sandler and D. D. Durigon, J . Phys. Chem., 69, 4201
(1965).
(19) W.W. Smeltzer, E. L. Tollefson, and A. Cambron, Can. J .
Chem., 34, 1046 (1956).
(20) J. T. Kummer, J . Phys. Chem., 63,460 (1959).
(21) H.B. Charmon, R. M. Dell, and S. S. Teak, Trans. Faraday
Soc., 59, 453 (1963).
 OF ETHYLENE
KINETICSAND MECHANISM OXIDATION
al
a
0
II
c
-
I packed into the other end of the steel tube. The
U used as a reactor feed composition. The analyses were
Figure 2. Typical chromatogram for isomerization of
ethylene oxide.
The vapor phase chromatograph was a Perkin-
Elmer Model 154D equipped with a thermistor de-
tector. Sampling was accomplished by means of a
Beckman gas sampling valve which contained two
calibrated 1.0-ml gas loops. The complete analysis of
the reaction gas mixture required a 1: 1splitting of each
sample between two parallel chromatographic columns.
Air, carbon dioxide, and ethylene were determined on a
silica gel column, while ethylene oxide and acetalde-
hyde were determined on a Kel-F on Fluoropak column.
When acetaldehyde was not required to be analyzed,
ethylene oxide was determined on a P,P'-oxydipro-
pionitrile on Chromasorb W column. Response factors
were determined for all reactants and products in order
to do quantitative analyses. A typical chromatogram
is shown in Figure 2. Samples removed approximated
1% of the total gas. Volume change corrections were
employed when required.
The entire system was kept under vacuum by a Welch
dual-stage mechanical pump with a liquid nitrogen cold
trap. All results were obtained a t reduced pressures in
order to give a proper sample size for the chroma-
1495
Product FWd
Sampling Sampling
Air ballast for
regulator - 75 ml. Surge
Vent
Reaction
Section Bath
Preieat Section
Flowmeterr
0
Hydracarbon AI,. 0 or
lend N*Pu& Feed
Both from pressure regulated cylinder rupply
Figure 3. Schematic diagram of ethylene oxidation
flow reactor.
tographic columns and also to avoid problems due to
the explosive limits of ethylene oxide and oxygen
mixtures.
Apparatus. Flow System. Figure 3 illustrates the
apparatus used for the oxidation of ethylene in the flow
reactor. The catalyst bed occupied 12 in. of the 0.635-
cm i.d. carbon steel tube used as a reactor. A preheat
section of 0.475-cm diameter alumina spheres was
catalyst bed volume was 9.7 cc. Flowmeters were
calibrated for delivery of the feed stream gases,
ethylene, and air at 50 psig.
At a flow rate of 100 cc/min of gas feed a t standard
conditions, a mixture of 55% ethylene and 45% air was
obtained by use of the same vapor phase chroma-
tograph as in the isomerization studies.
Materials. Chromatographic response factors were
obtained by the use of a pure sample of each reaction
component to be analyzed. The ethylene used was
Matheson CP grade gas and the carbon dioxide was
Matheson Bone Dry grade. The acetaldehyde was
Fisher CP, and the ethylene oxide was Matheson
(99.7%) compressed liquid distilled from the cylinder
into a cold trap. The same ethylene oxide was used as a
reactant in the isomerization studies. For the isomeri-
zation studies, Matheson Ultra-Pure analyzed oxygen
and Linde H. P. dry nitrogen were employed. Mathe-
son CP grade ethylene again was used for the oxida-
tion studies, as was Matheson dry compressed air.
Procedures. The studies of the isomerization of
ethylene oxide required premixing of the reactants.
Nitrogen was bled into the mixing bulb through a
needle valve and its pressure read on a vacuum test
gauge. Next the oxygen was bled into the bulb
through a needle valve and its pressure read by dif-
ference. Ethylene oxide was distilled under vacuum
from a cylinder at 26" to an aerosol test bottle thermo-
stated at 0". The bottle was warmed to above the
boiling point of ethylene oxide, 10.7", and some of the
gas bled into the bulb through a needle valve. The
Volume 74, Number 7 April 8, 1970
1496 ROBERT
E. KENSONAND M. LAPKIN

pressure was read to determine the concentration of Results

ethylene oxide just as those of oxygen and nitrogen had Nine experiments were conducted for the study of
been determined. The preheat section mas heated to the isomerization of ethylene oxide t o acetalde-
160" in the meantime. hyde. The results are summarized in Table I. A
The silver catalyst was oxygenated before each
experiment by maintaining 150 millimeters pressure of
oxygen in the closed reactor at the experimental tem- Table I : Kinetic Results for Ethylene Oxide Isomerization
perature for 1 hr. No change in the pressure of
oxygen was noted, yet when the catalyst bed was Expt [CzHiOIo, [0210/ ki X lo-*.
no. T,O C mm Io
[CZHIO seo-1
evacuated, adsorbed oxygen was removed from the
catalyst, as detected by the gas chromatograph. EO-1 200 33.4 4.03
Contacting the silver catalyst with oxygen for 5-6 hr EO-2 200 15.1 4.03
EO-3 200 18.3 3.83
did not affect the kinetic results; therefore, it was felt
EO-4 250 15.7 9.20
that the maximum amount of chemisorption of oxygen EO-5 250 16.4 8.78
on the catalyst was reached within 1hr. EO-6 250 16.8 8.48
To start a kinetic run, the catalyst bed was evacuated EO-7 250 9.6 9.17
t o as low a pressure as possible t o remove physically EO-8 285 17.3 19.3
EO-9 285 13.6 18.4
adsorbed oxygen and the toggle valve leading to the gas
sampling valve closed. The pressure was read on the kl av a t 200' = 3.96 X sec-I
vacuum test gauge attached t o the reactor after the kl av a t 250" = 8 , 9 1 X sec-l
reaction mixture was introduced and equilibrium kl av a t 285' = 1.89 X sec-l
attained; then the toggle valve to the preheat section
was closed. This was considered as time zero in the
reaction. Samples were then admitted into a sampling typical concentration us. time plot is shown in Figure 4.
loop and injected into the vapor phase chromatograph Kinetic run EO-1 was run under conditions similar to
at regular intervals. those employed by TwiggJ4 with oxygen absent.
Concentrations of reactants and products were de- Behavior similar to that observed by both Twigg4 and
termined by multiplying the area under a chroma- Ide7 was observed in this experiment. The major
tographic peak due t o a component by that component's product of ethylene oxide destruction was acetaldehyde,
response factor. The factors were found to be es- but some ethylene and carbon dioxide were formed.
sentially constant over the time period of these studies. When oxygen was preadsorbed and then excess
Calibration of the 1:l column flow split was accom- oxygen pumped off, as in all subsequent runs, the
plished daily by determination of the relative areas of ethylene formation was diminished. Runs EO-2 and
air peaks from the two columns.

-R.
For the studies of ethylene oxidation, the reactor
(Figure 3) was pressured up t o 50 psig and the flows
adjusted to give the proper gas feed composition. The
reactor was heated to 175" and the system allowed to
equilibrate overnight. A 1-cc sample of the exit gas
stream was then analyzed to obtain the yield of ethylene
oxide and the conversion of ethylene. The temperature
was raised and points taken until the selectivity of
ethylene oxide fell toward 50%,.
The selectivity for ethylene oxide was calculated from
the analysis of the exit stream ethylene oxide and car-
bon dioxide (eq 5a) while the conversion of ethylene was

10 -

calculated from the ethylene concentration at the

reactor exit as well as the ethylene oxide and carbon
dioxide concentrations (eq 5b).
Conversion (%) = 1000 2000 3000
(Seconds1

Figure 4. Plot of concentrations of reactants and products us.

time of kinetic run EO-1.

The Journal of Physical Chemistru

I<INETICS AND MECHANISM OF ETHYLENE
OXIDATION

EO-3 were conducted at about half the initial con-

Table 11: D a t a for Oxidation of Ethylene
centration of run EO-1 so that the order of the reaction
in ethylene oxide could be determined. The order, as Run Yield Conversion Conversion
no. T,OC C2H40, % C*Hir% 02, %
determined by plotting the log of the rate of initial
ethylene oxide loss us. the log of the initial ethylene 1 180 78 1.15 3.0
200 78 2.0 5.25
oxide concentration, was 1.03 f 0.04. In these two
210 76 3.8 10.45
experiments, oxygen was also added, equivalent to the 225 71 6.4 19.5
concentration of ethylene oxide. The major product 235 64 8.9 31.2
was then carbon dioxide, and the rate of its formation 245 59 10.0 35.6
was twice that of ethylene oxide disappearance. This 2 180 79 1.4 3.6
190 76 2.5 6.9
first-order rate law was obeyed through the first 90% of
200 73.5 4.15 12.0
reaction. 210 72 5.8 17.4
Four experiments, EO-4 through EO-7, were run at 220 69 7.6 24.2
250" to determine the rate of ethylene oxide isomeriza- 230 66 9.3 31.4
tion and oxidation at a higher temperature. Variation 240 62.5 10.8 38.6
3 175 81 0.6 1,4
of the initial ethylene oxide concentration confirmed 79.5 1.1
180 2.8
the first-order dependence in ethylene oxide. It was 190 77 1.85 4.95
also found, by varying the initial oxygen concentration 200 75 2.8 7.9
at constant initial ethylene oxide concentration, that 220 71.5, 5.3 16
the rate of oxidation of ethylene oxide is independent of 225 69.5 5.9 18.6
245 59 9.7 37
the oxygen Concentration. Two more experiments were 4 175 80 0.95 2.4
run at 285" and the results were consistent with the 180 79 1.35 3.45
previous results. 190 75 2.0 5.75
Thermodynamic variables were then determined from 200 74 3.2 9.2
the kinetic data. Pressure measurements before and 210 72 4.4 13.2
215 69 5.5 17.5
after t = 0 indicated that the adsorption of ethylene 220 68 18.9
5.8
oxide on the catalyst was very small in magnitude. 225 64 6.6 23.1
The desorption of product was rapid enough that the 240 64 7.4 25.9
rate of reactant disappearance was equal to the rate of 245 63 7.4 26.4
product formation; therefore, the surface concentration 5 175 80 0.95 2.4
180 79 1.2 3.1
of chemisorbed species would be low. It was then
190 79 2.0 5.1
possible to express the thermodynamic variables in a 200 72 3.5 10.5
simple Langmuir-Hinshelwoodzz form rather than 210 69 5.3 16.8
having recourse t o an Elovitch isotherm.23 The 220 67.5 6.6 21.6
energy of activation for isomerization of ethylene 235 64.5 9.8 34.1
245 63 10.2 36.4
oxide, E,, was 9.8 k 0.6 kcal/mol, and the enthalpy of
activation at 200, AH*2ooo,was 8.9 * 0.6 kcal/mol. 6
250
175
61
80
11.2
0.9
41.5
2.25
The value of the entropy of activation, AS*, as de- 190 75 2.3 6.5
termined from the 200" data mas found to be -56 * 2 200 73.5 3.8 11.o
eu. The oxidation of ethylene to ethylene oxide and 210 71 5.8 17.6
carbon dioxide and water was also studied. In each 225 69 7.8 24.8
235 68 8.7 28.3
experiment a new catalyst bed was utilized; therefore 240 65 9.4 32.3
the results (Table 11) show some variance. Orzechow- 250 61 10.5 38.7
ski and McCormacks noted that prolonged periods of 7 175 82.5 0.65 1.5
ethylene oxidation were required to bring such catalysts 180 81 0.9 2.2
to equilibrium. The high selectivity of the ethylene 190 77.5 1.45 3.85
200 77 2.5 6.7
oxidation was shown by the fact that over a tenfold 210 74.5 3.6 10.25
increase in per cent ethylene reacted and over a 65" 225 73 6.0 17.6
temperature range, the ethylene oxide selectivity only 240 69 8.0 25.5
decreased from 79% to 59%. This could be shown 250 63 9.3 33.2
by a plot of conversion of ethylene us. ethylene oxide
selectivity as shown for run 1in Figure 5.
I n fuel-rich oxidations, such as that of ethylene in chowski and McCormack treatment6 (6) will approach
this study, the reaction order approaches zero in the first-order case (7).
ethylene and 1 in oxygen for both ethylene oxide and
carbon dioxide formation. At an ethyleneloxygen (22) I. Langmuir, J . Amer. chem. soc., 40, 1361 (1918).
ratio of over 6 , the rate equation in terms of the Orze- (23) M.J. D.Low, Chem. Rev.,60, 267 (1960).

Volume 74, Number 7 April .2* 1970

1498 ROBERT
E. KENSON
AND M. LAPKIN

Table 111: Typical Results for the Rate of Ethylene Oxide Formation
Run no. 1 2 3 4 5 6 7 Av

kl x 1 0 2 a t 2 0 0 ~ 0.59 1.25 0.82 0.94 1.01 1.14 0.71 +

0.91 0.24
kl X 102 at 2250agb 2.82 ... 2.26 3.70 ... 4.24 2.33 3.07 =k 0.94
a kl obtained from In [0%]0/[02]
t = ( 0 . 5 kl + 1 . 5 kz)t where t = 16 sec and kl = ~ Q H ~ Okz, = kcoz. * In sec-l.

/\CHZ-CHZ
& /\
CHZ-CHZ
(chemisorbed) (sa)

k
- [02] = k[02l
/\ (chemisorbed) 2
k CH3-C,H //o (ads) (8b)
B CH*--CHP I

k 40
CH3-C<o H (ads) A CH3- cH
,

The reaction would be pseudo-zero order in ethylene

at this ethylene-oxygen ratio of 6, as only 10% or less
of the ethylene mas reacted during any kinetic run.
Equation 6 has been applied successfully to other
studies of ethylene oxidation where fractional orders in
ethylene and oxygen are encountered. Absolute rate
constants for ethylene oxide formation were determined
from (8) which follows from (7) and the reaction
In ( [ 0 2 1 0 / = ( O . ~ ~ C ~ H4,-O 1 5kc0&
I (8)
stoichiometries ( 1 ) and (2). The reaction is first order
in oxygen and approximately zero order in ethylene for
both ethylene oxide and carbon dioxide formation.
Variations at constant T were about *30% (Table
111), consistent with behavior encountered in many
kinetic studies of ethylene oxidation.
Calculation of activation energies from each experi-
ment for ethylene oxide formation indicated that con-
sistent results could be obtained from each set of
kinetic data, which gave an average value of 21.4 f 0.8
kcal/mol.
The activation energy for carbon dioxide formation
was obtained from the relative rate data (IC relative =
~ C ~ H ~ O / ~ C OA
J . plot of the log of IC (relative) os. 1/T
was made to determine AEa, where AEa is Ea C~H,O -
Eacoxand k (relative) is C2H40selectivity/2(100-C~H~O
selectivity). AEa was determined to be -7.6 f 1.5
kcal/mol; therefore, the average E, for carbon dioxide
formation is 29.0 f 1.7 kcal/mol as determined by
subtraction of AEa from the E , for ethylene oxide
formation. Avalue for A S C ~- ~ *
ASCO~*,
~ ~ or AAS*, of
-10.4 eu was determined from the same relative rate
data.
Discussion
Two mechanisms to explain the kinetic data for the
isomerization and oxidation of ethylene oxide are
proposed. Thermodynamic data were used to establish
the most reasonable one. The first mechanism
(designated above as reactions 8a-8d) postulates
CH3-C, / / 0
H
+ 0 2 A
k
coz +
k2, k4>> k2 rate = K , k 2 [cH,-cH,~
?\
that the rate-determining step is the isomerization of
ethylene oxide adsorbed on the catalyst to acetalde-
hyde. This step would be preceded by rapid chemi-
sorption of ethylene oxide on the catalyst. The
acetaldehyde would then be oxidized by oxygen to
carbon dioxide and water. The value of the apparent
AS*, which in this case ~7ouldbe the sum of A& +
AS2 *, is quite reasonable in relation to literature values
for chemisorptive p r o c e s s e ~ . ~ In
~ - order
~ ~ to rationalize
the value of Ea,less reasonable partitionings of energy
must be employed. In order for Ea to be about 10
kcal/mol, ql, which is the sum of p adsorption q +
chemisorption, must be negative and at least of the
order of magnitude of Ea
Ea Ea (true) + pi (9)
but q adsorption should be approximately thermo-
neutral.27 Q chemisorption would, therefore, have to
be at least about 10 kcal for mechanism 8a-8d to be
valid. Since ethylene oxide is only very weakly
adsorbed28~29and q chemisorption is therefore small,
(24) AS1 is the entropy change for the equilibrium chemisorption
(K1)and AS2 f is the entropy of activation for the isomerization.
Chemisorptive entropies determined for ethylene on copper and
gold,zSfor example, are -33.4 and -42.5 eu a t low surface coverage
(8 = 0.1). The same magnitude of equilibrium entropy should be
obtained for the chemisorption of ethylene oxide on silver. The
entropy of activation for the ethylene oxide isomerization should be
close to that for thermal isomerization of ethylene oxide to acetal-
dehyde,*e which is - 1.98 eu.
(25) B. M. W. Trapnell, Proc. R o y . Soc., A218, 566 (1953).
(26) M. L. Neufeld and A. T. Blades, Can. J . Chem., 41,2956 (1963).
(27) A value of q isosteric can be computed from data on kinetic
runs a t 200 and 250 where the surface coverage, 8, was approxi-
mately constant. Application of the Clausius-Clapeyron relation
yielded a value of p = -2.3 kcal/mol.
(28) J. A. Allen and P. H. Scaife, Aust. J . Chem., 20,837 (1967).

The Journal of Physical Chemistry

KINETICS
AND MECHANISM
OF ETHYLENE
OXIDATION
this route for oxidation of ethylene oxide is unsatis-
factory.
CHp-CH, (ads) 'low
/"\
CH2-CH2 (chemisorbed)
(lob)
rate = K a k ,
?\
[CH2-CH21
hz, ha, h4>>hl
The second mechanism (eq loa-10e) involves the
same sequence of steps as (8a-8b), except the rate-
determining step is postulated as the chemisorption
(lob) of ethylene oxide on the catalyst. This assumes
that the isomerization to acetaldehyde is rapid and that
desorption of chemisorbed ethylene oxide is not sig-
nificant. The chemisorption of a molecule on a
catalyst has been shown in many cases to be an acti-
vated process,ls and therefore it can be the rate-deter-
mining step in a heterogeneous reaction. The low
value for the activation energy would be consistent
with this mechanism. The high negative value of
A S * (-56 f 2 eu) is quite common with activated
chemisorption, especially in the case of a very localized
reactant-catalyst site complex.sO The activated com-
plex can be depicted as a silver atom bonded through
oxygen to the ethylene oxide.
">C-C /H
\0/ "
I (29) Allen and Scaife reported a nonactivated process similar to
All translational entropy would be lost, as well as some
of the rotational entropy.24
The most consistent explanation of the kinetic and
thermodynamic data, therefore, is that the rate-de-
termining step of the isomerization and subsequellt
oxidation of ethylene oxide is activated chemisorption
investigations.6*s
1499
EO 65 70 75
Selectivity of C2H40,%.
Figure 5. Conversion-yield plot of data from run 1.
As the rate-determining step is the activated chemi-
sorption, the subsequent isomerization step is fast
enough to account for the quantity of carbon dioxide
produced by ethylene oxidation.31 The reactivity of
chemisorbed ethylene oxide toward isomerization t o
acetaldehyde accounts for the rate of formation of
carbon dioxide and the concomitant loss of ethylene
oxide yield in the oxidation of ethylene. This is
equivalent to merging reactions 2 and 3 of the gen-
eralized ethylene oxidation mechanism.
The relevancy of this study t o previous work should
be obvious. Previous investigators6i6concluded that
because of the slow rate of ethylene oxide isomerization
to acetaldehyde, this was not an important route of
carbon dioxide formation in ethylene oxidation over
silver. This conclusion was founded upon the incorrect
assumption that the rate-determining step of ethylene
oxide isomerization was the isomerization reaction.
Further evidence in support of the conclusions
reached in this study was obtained by employing the
same catalyst for the oxidation of ethylene. The
activation energy determined for ethylene oxide forma-
tion (21.4 kcal/mol) appeared to fit previous re-
sults.s~1a~a2 The activation energy varies from catalyst
to catalyst because of the presence of promoters,
intentional or unintentional, in the silver. Twigg,
with a silver catalyst deposited on glass wool, obtained a
value of 23 kcal/mol. The measured activation energy
for ethylene oxide formation is dependent on both the
that observed by Twiggaf4and the present authors. The major route
of ethylene oxide adsorption betveen 250 and 373OK was an activated
process. Quantitative comparisons with higher temperature studies
may not be possible because of catalyst differences and the use of a
different form for the adsorption isotherm than used in many of the
studies of ethylene oxide adsorption on s i l ~ e r . ~ , ~ J
(30)~Calculationof AS* from a localired complex model (11) for
the lnteraction of silver and ethylene oxide confirms the nature of
*
the ethylene oxide adsorption on silver, as the A S calculated from
the model is -58 j= 12 eu while the experimental value is -56 f 2
(32) J. T. Kummer, J. Phys. Chem., 60, 666 (1956).
Volume 74, Number 7 April 2 , 1970
1500 ROBERTE. KENSONAND M. LAPKIN

purity of the silver catalyst, where unintentional This results in the formation of ethylene oxide and
promoters may be present, and the rate-determining Ag,O, which is the most probable configuration of the
step, as the measured activation energy is a sum of atomic oxygen-silver complex. This complex is also
several equilibrium heats of reaction and the true reactive to ethylene, but leads to a formation of ethylene
activation energy in a catalytic reaction. We would oxide in a chemisorbed state (13)
presume then that the Tmigg studies involved basically
the same catalyst and rate-determining step as the
present study, The activation energy for carbon
dioxide formation in the present study was calculated
to be 29 kcal/mol, The difference in activation
energies between the reactions leading to carbon dioxide
and to ethylene oxide is only 7.8 kcal/mol. Such a
difference is not surprising, as the selectivity to ethylene
oxide from the oxidation of ethylene only varied from
about 80% to 60% over a 80-70" temperature range.
It has been proposed in the past that the two reactions,
1 and 2, involve the same transition state and are
identical in most reaction steps except for their final Isomerization of the chemisorbed ethylene oxide to
products. The difference in activation energies be- acetaldehyde occurs quite easily (14) and the resultant
tween the ethylene oxide and carbon dioxide forming acetaldehyde is rapidly oxidized to carbon dioxide and
reactions, however, precludes a common transition water, as shown by the ethylene oxide isomerization
state. The selectivity is higher than in many other studies.31 High yields of ethylene oxide are obtainable
studies of ethylene oxidation because of the low ethylene in spite of the apparent prediction by the proposed
conversion (l--lO%) and high pressure (50 psig) mechanism of a limiting yield of 50%. One factor is
employed. Good agreement was obtained with the the higher reactivity of the ethylene oxide-forming
ethylene oxide selectivity results of Twigg at low
ethylene conversion. The large difference in activa-
tion energy between ethylene oxide and carbon dioxide
formation indicates that a different rate-determining
step may be found in the present study.
I s o t o p i ~ ~and
~ - ~gravimetric
~ methods have proven
the existence of two major oxygen species on the
catalyst surface, one molecular (0-0 bonds present)
and one atomic (0-0 bonds absent) in nature. Any
mechanism proposed for the oxidation of ethylene
therefore has to meet the criteria of accounting for: (I),
the high selectivity of the reaction; (11),the roles of the
HgC-CH,
two different oxygen species present on the catalyst;
(111), the activation energy difference in the two ethy- \0/
lene oxidation routes; and (IV) the ethylene oxide Ag Ag
isomerization results.
The most logical explanation is that the formation of
ethylene oxide occurs by reaction of ethylene with the /O\
molecular oxygen-silver complex (12) analogously to catalyst sites, relative to the Ag Ag sites. The
liquid phase oxidation of olefin^.^^-^^ lower reactivity of the atomic oxygen complex results
from its facile migration to form AgzOz complexes by
recombination with another AgZO complex. The
activation energy for this step is lower than for reaction
with ethylene. A second factor is the competition of

(33) The exact structure and stoichiometry of the molecular oxygen

silver complex is not known. Stoichiometries of AgOz, AgzOa, and
AgzOz have all been reported in the literature,a4--96 The structure of
">C-C /H Ag20z does not infer in our mechanism an exact structure, but simply
a peroxidic silver-oxygen species.
\01" (12) (34) M.W. May and J. W. Linnett, J . Catal., 7, 324 (1967).
(36) Von M. Feller-Kniepmeier, H. G. Feller, and E. Titzenthaler,
Be?. Bunsenges. Phys. Chem., 71, 606 (1967).
(36) L. Ya. Margolis, Advan. Catal., 14, 463 (1963).

The Journal of Physical Chemistry

 OF ETHYLENE
KINETICSAND MECHANISM OXIDATION
(A320 + OI$ I ethylene oxide formation. The value of energy level B,
Figure 6. Thermodynamic diagram for ethylene oxidation.
the desorption (15) of chemisorbed ethylene oxide with
the isomerization of ethylene oxide (14). A third
factor is the higher proportion of peroxide sites, only a
fraction of which have reacted in any given time interval
to produce Ag20 sites. Higher pressures of oxygen or
the use of selective poison (small concentration of an S or
C1 containing compound) would then decrease the rate
of isomerization of chemisorbed ethylene oxide because
the oxygen or selective poison would be able to effec-
tively compete for the silver catalyst site adjacent t o the
chemisorbed ethylene oxide.
Thermodynamically, the difference in activation
energies for the two reactions is related to the stabilities
of the two oxygen-silver complexes. Ethylene adsorp-
tion is very weak; therefore, it will contribute little to
the activation energies. The thermodynamic diagram
for oxygen-silver systems is found in Figure 6.
The values for the thermodynamic variables, such as
the heat of activation for AgzO decompo~ition,~~ the
activation energies for oxygen adsorption and mobility, l6
and the heat of oxygen adsorption,8swere obtained from
the literature. The heat of formation of AgzO was
obtained from NBS data.S9
The activation energy difference between the ethylene
oxide and carbon dioxide forming reaction will depend
upon the stabilities of the oxygen-silver complexes and
the transition states for their decomposition. From
the data, it is apparent that the Agz02 species is 8
kcal/mol more stable than AgzO. The Ag202transition
state, however, is about 17 kcal/mol lower in energy
than Ag2O as determined from Czandernas data.16z40
The higher the transition state energy, the higher is
the activation energy. From the equation AE, =
A E t r a n a i t ion state - AEground state, was calculated as
-9 kcal/mol, in good agreement with the experimental
value of -7.6 f 1.5 kcal/mol determined in this
study. The absolute values for the activation energies
1501
for ethylene oxide and carbon dioxide formation were
determined from the data, Figure 6. The value of
energy level A, 21 kcal/mol, was equivalent t o the
activation energy for formation of ethylene oxide from
ethylene and Ag20z,and it compared well with a value
of 21.4 kcal/mol calculated from the kinetic data for
30 kcal/mol, was equivalent to the activation energy
for ethylene oxide formation from ethylene and Ag20,
and was very close to the value calculated from the E,
for ethylene oxide formation minus AE,, 29 kcal/mol.
This is also comparable with the previously determined
value of the heat of activation of Ag20decomposition of
28 kcal/mol. 37
The resultant values for the activation energies of
ethylene oxide and carbon dioxide formation are
unfortunately not uniquely determined by use of
reactions 12-15. Using the same thermodynamic
diagram, reasonable values for these respective activa-
tion energies can be calculated for several alternative
mechanisms for ethylene This
mathematical exercise does, however, lead to the con-
clusion that the rate-determining step for ethylene
oxidation to either ethylene oxide or carbon dioxide and
water involves primarily the breaking of one or more
silver-oxygen bonds. This means that except for the
extreme cases, ([CzH4]>> [Oz] or 102.1>> [C2H4]),the
surface reaction of a silver-oxygen complex with
adsorbed ethylene is rate determining in the oxidation
of ethylene to ethylene oxide or carbon dioxide. The
*
value of AAS indicates that the oxidation of ethylene
to ethylene oxide has a more ordered transition state
than oxidation to carbon dioxide. This evidence
would favor ethylene oxide arising from reaction of
ethylene with a molecular oxygen-silver complex. I t
is possible that preferential adsorption at kink and
ledge sites would lead to this negative AAS*:.42
In summary, the selectivity of the reaction is ex-
plained by the coupled nature of the reactions. The
activation energy difference of the two oxygen species
involved in these reactions is related to the difference in
their thermodynamic stabilities and those of the
(37) B. D. Averbukh and G. I. Chufarov, Zh. Fiz. Khim., 23, 37
(1949).
(38) A. F. Benton and L. C. Drake, J. Amer. C h e m Soc., 56, 255
(1934)I
(39) Selected Values of Chemical Thermodynamic Properties,
National Bureau of Standards Circular No. 500, U. S. Government
Printing Office, Washington, D. C., 1950.
(40) The relative energy state of [AgaO]* was calculated as equal
to the difference in activation energies between molecular and atomic
adsorption on silver, this 5 kcal/mol being taken as equivalent
/O\
to the energy for forming [Ag Ag]*. The relative energy state
of [Agz + 01 was taken to be equal to the activation energy required
for migration of an oxygen atom, 22 kcal/mol.
(41) H. H. Voge and C. R. Adams, Advan. Catal., 17, 171 (1967).
(42) 0. Knacke and I. N. Stranski, Progress in Metal Physics,
Vol. VI, Pergamon Press, London, 1956, pp 214-216.
Volume 74, Number 7 April 8 , 1970
1502 Z. M. GEORGEAND H. W. HABGOOD

transition states. By examination of the relative
activation energies, it was determined that the ethylene
oxide formation is caused by reaction of ethylene with
the molecular oxygen-silver complex. Carbon dioxide
can then be produced by reaction of ethylene with the
atomic oxygen-silver complex which forms. This
gives a chemisorbed ethylene oxide, which can rapidly
isomerize to acetaldehyde and subsequently is oxidized
to carbon dioxide and water. The reaction of these
silver-oxygen complexes with adsorbed ethylene is the
rate-determining step in the oxidation of ethylene to
ethylene oxide or to carbon dioxide and water.
Acknowledgments. The authors wish to thank the
Vapor Phase Chromatography Laboratory, Analytical
Department, for the development of the analytical
separations. We thank Mr. Roger Polak for the flow
system experimental results. The authors also wish to
express their appreciation to Dr. John Churchill for
many helpful comments and stimulating discussions.

Mechanism of the Catalytic Isomerization of Cyclopropane

over BrrlJnstedAcid Catalysts'

by Z. M. George and H. W. Habgood

Research Council of Alberta, Edmonton 7, Alberta, Canada (Received September $2, 1969)

The isomerization of cyclopropane over a BrZnsted acid catalyst takes place via a protonated cyclopropane
intermediate, which on ring opening gives propylene probably through a primary propyl cation. With a
deuterated catalyst the propylene product is randomly deuterated and, for a fully deuterated catalyst, the
extent of monodeuteration during isomerization is 8501,, which is close to e/7 as expected for complete mixing
with no isotope effect of one D with 6 H's. These results suggest that the c-CsHeD+ion probably has
sufficient time to equilibrate among its various isotopic forms before the ring opens. A lower degree of deutera-
tion during the isomerization step may be found if the catalyst is incompletely deuterated, and this was found
to be the case for NaY catalyst equilibrated with DzO at 300". Some catalytically active sites which do not
readily exchange with D20 form a significant fraction of the acid sites on a catalyst of low acidity such as Nay.
These peculiar sites are of negligible importance in practical catalysts such as NaHY aeolite which have much
higher total acidity.

Introduction are probably the result of some hydrolysis of the

The mechanism of the Brplnsted acid catalyzed iso-
merization of cyclopropane to propylene is of interest
in connection with current studies of this reaction
as a possible test reaction for measuring catalyst
Brqhsted acidity. A previously published study from
this laboratory2 had given results inconsistent with
what is probably the simplest mechanism
+ hydrogen atoms exchanged per molecule gave a value
[CHz-CHZ-CH,D] CH2=CH-CH2D
In these experiments slugs of cyclopropane were passed
over an NaY zeolite catalyst that was maintained in
deuterated form by a low 'Onstant pressure
of D20. The catalytic sites on the sodium zeolite
sodium ions and also some crystal defects. It was
found that about 26% of the propylene produced
by the isomerization reaction did not have any deu-
terium whereas eq 1 would lead to 100% exchange
during the isomerization step. To account for these
results, Bartley, Habgood, and George2 proposed two
alternative mechanisms, each involving an intramolecu-
lar hydride transfer during the ring-opening step.
Meanwhile, Hall and Hightower? carried out a differ-
ent sort of experiment in which the coisomerization
of a 50: 50 mixture of cyclopropane-& and cyclopro-
pane-& over silica-alumina was studied. A plot of
+ H" (1)
of between 0.45 and 0.50 on extrapolation to zero
CoI1VerSion, and this indicated that there was One?
(1) Contribution No. 475 from the Research Council of Alberta.
(2) B. H. Bartley, H. W. Habgood, and 2. M. George, J. Phys.
Chem., 72,1689 (1968).

The Journal of Physical Chemistry