Вы находитесь на странице: 1из 22

Chem. Eng. Commun. Vol. 44 pp. 53-74 0098-644518614406-0053$25.00/0 0 1986, Gordon and Breach Science Publishers S.A.

Printed in the United States of America.

MICHAEL STOUKIDES Department of Chemical Engineering, Tufts University, Medford, MA 02155 and STAVROS PAVLOU Department of Chemical Engineering, University of Patras, Patras 261 10, Greece
(Received June 10, 1985; in final form December 9, 1985)

Ethylene oxidation to ethylene oxide and to carbon dioxide over silver catalysts was studied in a CSTR. The effects of two factors on the catalyst performance were examined. The first was the presence of excess ethylene oxide in the feed. A kinetic model was introduced which assumed that ethylene and ethylene oxide compete for the same sites on the catalyst surface. This model provided reasonable quantitative agreement with kinetic and potentiometric measurements. The second factor that was studied was the presence of external heat and mass transfer limitations. It was found that such limitations cause a significant decrease of the selectivity to ethylene oxide. This decrease is a result of the temperature difference between the catalyst surface and the bulk of the gas phase and of the fact that the activation energy of ethylene combustion is greater than that of ethylene epoxidation. The contribution of other factors such as inhibition by CO, o r possible incomplete mixing in the reactor is shown to be insignificant. KEYWORDS Catalytic ethylene epoxidation Ethylene oxide selectivity Solid electrolyte potentiometry Oxygen activity measurement Selectivity of polycrystalline silver External transfer limitations

INTRODUCTION Ethylene oxide is produced commercially from ethylene oxidation over supported silver catalysts. There is a general consensus (Sachtler et al., 1981; Voge and Adams, 1967), that the kinetics can be described by means of a triangular scheme:
5( +

CzhO h y y(+3oJ


12(+301)- 2 [COZ+ H@l

The activation energies and reaction orders for the three reactions have been investigated by numerous groups and their results have been summarized by



Voge and Adams (1967), Kilty and Sachtler (1974) and recently by Sachtler, Backx and Van Santen (1981) as well as by Barteau and Madix (1982). A number of parameters that affect the selectivity to ethylene oxide (moles of ethylene oxide produced per mole of ethylene consumed) has been reported so far including halogen compounds (I(ilty and Sachtler, 1974; Kilty et al., 1972), crystal size and orientation (Kummer, 1956; Harriot, 1971; Johnson and Verykios, 1983) as well as y-preirradiation (Carberry, 1972). The inhibiting effect of reaction products and other species on the reaction yield and selectivity has also been studied extensively (Voge and Adams, 1967; Sachtler el al., 1981; Cant and Hall, 1978; Hayes, 1960). Nevertheless, despite the large number of investigators and some very interesting recent experimental findings (Wachs and Kelemen, 1981; Ghazali et al., 1983; Campbell and Paffett, 1984; Haul et al., 1984; Grant and Lambert, 1985(i), 1985(ii)) no generally accepted reaction mechanism has been established. The very wide scatter of the published parameters make it impossible to draw unambiguous conclusions on the mechanism from such data. The present communication is focusing attention on a) the effect of ethylene oxide on the reaction rates and b) the effect of external diffusional effects on the catalyst activity and selectivity. Conflicting results exist so far on the role of ethylene oxide on the reaction selectivity. A linear decrease of the selectivity with increasing ethylene oxideloxygen ratio has been reported by Temkin and his co-workers (1962; 1979). Force and Bell (1975) however observed an increase in selectivity with increasing ethylene oxide concentration although this increase was not permanent. In the present work kinetics are combined with in situ electrochemical measurement of the activity of oxygen adsorbed on the catalyst surface using the technique of Solid Electrolyte Potentiometry (SEP). This technique has already been used in conjunction with kinetic measurements in order to study the mechanism of various catalytic oxidations (Vayenas et al., 1981; Stoukides and Vayenas, 1980; Stoukides and Vayenas, 1981). Reactor cells similar to the one used in this study have been used so far to enhance the rate of NO decomposition and C O hydrogenation (Pancharatnam et al., 1975; Giir and Huggins, 1981), as well as in high temperature fuel cells (Etsell and Flengas, 1971; Vayenas and Farr, 1980). EXPERIMENTAL METHODS A schematic diagram of the experimental apparatus is shown in Figure 1. It consists of the flow system, the reactor cell and the analytical system. The reactor cell was a 8% yttria stabilized zirconia tube of 2cm2 cross sectional area and 30cm3 volume. The Ag catalyst film was deposited on the flat bottom of the zirconia tube. A similar Ag film was deposited on the outside bottom wall of the reactor as shown in Figure 2. This film was exposed to air and sewed as the reference electrode. T o deposit the film, a few drops of a silver suspension in butyl acetate (Stoukides and Vayenas, 1980) was used, followed by drying and calcining at 400C. The Auger spectrum of the catalyst showed (Stoukides and


S c h m t i c nlagran of A"paratur


Infrared Cn2 h a l y z e r
Gar Chmratnsraph
lcmpcraturr C o n t r o l l e r

Dlff~rentlal V o l t m e t e r

FIGURE 1 Schematic diagram of apparatus

Ag w i r e

FIGURE 2 Schematic diagram of reactor cell



Vayenas, 1980) that the silver surface was fairly clean. Trace impurities including some CI (less than 1 % of a monolayer) might have been responsible for the relatively high selectivities obtained. The catalyst surface area was estimated using oxygen chemisorption followed by reaction with ethylene as it has been described in detail elsewhere (Stoukides and Vayenas, 1980). It was thus found that the catalyst could adsorb approximately 1.8 x moles of oxygen at 300C. A silver wire, enclosed in a pyrex tube was used to make contact with the internal Ag film catalyst-electrode (Figure 2). The reactor temperature was controlled within 2C by means of a Leeds and Northrup temperature controller. A J. Fluke voltmeter was used to monitor the open-circuit EMF of the cell. Matheson certified gases (ethylene oxide, ethylene, oxygen) diluted in nitrogen were used as reactants. The feed and product composition was determined by means of a Perkin-Elmer Gas Chromatograph with a TC detector. A molecular sieve 5A column was used to separate N2 and O2 and a Porapak Q was used to separate air, C 0 2 , ethylene and ethylene oxide. The CO, concentration in the products was also monitored by a Beckman 864 Infrared Analyzer. Measurement of Surface Oxygen Activity The technique of Solid Electrolyte Potentiometry (SEP) provides a continuous in situ measurement of the thermodynamic activity of oxygen adsorbed on the catalyst surface. It has been established (Wagner, 1970; Stoukides and Vayenas, 1980), that the open circuit EMF of the cell reflects the difference in chemical potential of oxygen adsorbed on the two silver electrodes:

E = -[po,(Ag catalyst) - po,(Ag reference)]

1 4F


The chemical potential of oxygen adsorbed on the reference electrode which is in contact with air (Po, 0.21 bar) is given by

(2) where &(g) is the standard chemical potential of oxygen at the temperature of interest. The activity a, of adsorbed oxygen can be defined by: Thus a; expresses the partial pressure of gaseous oxygen that would be in thermodynamic equilibrium with oxygen adsorbed on the catalyst surface, if such an equilibrium were established. Therefore, combining Eqs. (I), (2), and (3) one obtains: a, = ( 0 . 2 1 ) ' ~ exp The above equation is always valid, irrespective of whether thermodynamic equilibrium is established between gaseous and adsorbed oxygen or not. In the special case where thermodynamic equilibrium indeed exists between adsorbed and gaseous oxygen, then a: = Po,.

po,(Ag reference) = &(g)

+ RT ln(0.21)




The catalytic oxidation of ethylene was studied in presence of excess ethylene oxide in the feed stream at temperatures 280-400C and atmospheric total pressure. Under the flowrates employed in this study, it has been shown (Stoukides and Vayenas, 1980) that the reactor is well mixed (CSTR). Absence of external or internal diffusional effects has been established in previous studies using the same reactor under similar temperature and Bow conditions (Stoukides and Vayenas, 1981). The rate of net production of ethylene oxide (in moles of ethylene oxidels) was calculated from the raw kinetic data using the appropriate mass balance

where x ~ ~ 0 . and i " XETO,,,, are the mole fractions of ethylene oxide in the feed and outlet respectively and G is the total molar flowrate. Due to the dilution of the reactants in N, the change in G from the stoichiometry of the reactions was less than 1% and hence G was considered constant. The rate of CO, formation r o , was calculated from the steady state material balance:

The rates of ethylene oxide formation, ethylene deep oxidation and ethylene oxide oxidation have already been studied-in absence of excess ethylene oxide in the feed-using the same apparatus, reactor and catalyst preparation (Stoukides and Vayenas, 1980; 1981). It was found that for excess air in the reactor the three reaction rates could be described rather accurately by the equations:

The validity of Eqs. (7) through (9) was verified by repeating the experiments at temperatures 280-400C. The values of the rate constants K , , K,, K 3 , K,, KETo that best fit the experimental data were:


KETo = 3.3 X lo-' e x p ( l )



i.e. very close to the values reported previously. The effect of excess ethylene oxide in the feed stream on the rate of C 0 2 formation rc0, as well as on the net rate of ethylene oxide formation rET, is shown in Table I. Each one of the data resulted from the average of two measurements. The partial pressure of ethylene oxide in the reactor varied from
Effect of ethylene oxide on reaction rates



FIGURE 3 Rate o f CO, production vs. P,,,,.

Po, = 0 . l bar, P,., =O.OlOS bar

FIGURE 4 Rate of ethylene oxide formation vs. P,,,.

Po, 1 0 . 1 bar, PET=0.0105 bar.



0.0006 to 0.024 bars while the partial pressure of ethylene and oxygen were kept constant (within 5%-10%). Figure 3 shows the effect of ethylene oxide on rco, Only a slight increase is observed with increasing PETO at all temperatures examined. The corresponding effect of ethylene oxide on rETo is shown in Figure 4. A considerable decrease on rETo with increasing PETO is observed, the effect being more important at high temperatures. Finally, the surface oxygen activity an was found to depend on PETO in the way shown in Figure 5. At all temperatures examined, a, seems to depend very weakly (slightly decreasing) on PET,. In a separate set of experiments the effect of external transport phenomena on the selectivity to ethylene oxide was studied. First, it was necessary to determine the range of flowrates within which external transport phenomena became dominant. To this end, the rate of ethylene consumption was measured while varying the total volumetric flowrate between 160 and 720cm3/min at 440C. Ethylene oxide was not introduced in the feed. The data are shown in Figure 6,

FIGURE 5 Dependence of surface oxygen activity on P,,,.

P,,=O.l bar, PET=0.0105bar.


FIGURE 6 Effect of volumetric flowrate on the rate o f ethylene consumption. T=440"C, Po, = 0.1 bar.

where the ratio APETIPET is plotted vs. the reciprocal flowrate l / Q . Here PET is the partial pressure of ethylene in the reactor and APET = PET,; - PET,where PET,i is the partial pressure of ethylene entering the reactor. At 440C both rates rl and r2 (Eqs. (7) and (8)) are practically first order in ethylene (Stoukides and Vayenas, 1981). Hence, one may write


and consequently:

Therefore, in absence of diffusional effects, APETIPET plotted vs. Q-' should give a straight line. It can be seen in Figure 6 that this is true for flowrates greater than 250 cm3/min. At 440C and for Q values lower than 250 cm3/min, transport phenomena have a significant effect on the measured reaction rates. The effect of external transport phenomena on the selectivity (S) to ethylene oxide was studied by measuring reaction rates at various flowrates. Results are summarized in Table I1 for 400 and 440C. The rates r, and r2 were calculated


TABLE 11 Etfect of flowrate on reaction rates and selectivity

from the equations:

Q r , = r , - r --PETO '-RT

The approximations in the above equations were based on kinetic data reported previously (Stoukides and Vayenas, 1980, 1981), which indicate that the rate r3 is negligible compared to the rates r, and r2. The selectivity S was calculated as

The effect of Q on r, and r2 as well as on S is shown in Figures 7 and 8. With decreasing flowrate, both rates r, and r2 decrease (Figure 7 ) , but the decrease in r, is larger than the decrease in r2 and thus the selectivity decreases (Figure 8).


FIGURE 7 Effect of volumetric flowrate on rates of ethylene oxide and CO, formation. P,, = 0,005-0.0067 bar, Po, = 0.085 bar.

FIGURE 8 Effect of volumetric flowrate on reaction selectivity. Po, = 0.085 bar, P, = 0.0050.007 bar.



In a ~ r e v i o u s communication (Stoukides and Vayenas, 1981) a kinetic model for ethylene oxidation on polycrystalline silver films was proposed. The experimental results resented here were obtained under similar temDerature and gas com~osition and with the same reactor. Moreover, the catalyst preparation was identical to that followed previously (Stoukides and Vayenas, 1980, 1981). According to the previously presented kinetic model two types of adsorbed oxygen are assumed, i.e. molecular, being responsible for the ethylene epoxidation and atomic, being responsible for C 0 2 and H 2 0 formation. Ethylene and ethylene oxide were assumed to compete for the same sites following Langmuir adsorption kinetics. Ethylene oxide was considered to adsorb primarily as a dimer (Stoukides and Vayenas, 1980). However, since under the reaction conditions the partial pressure of ethylene oxide was very small (PETo<&PET) the coverage of ethylene adsorbed on the catalyst was calculated from the following equation:

This is valid only for OETo = 0. Excess oxygen was used in all the experiments, so that the rate expressions for epoxidation and deep oxidation to C 0 2 were given by Eqs. (7), (8) and (9). Finally, in agreement with previous studies (Sachtler et al., 1981; Cant and Hall, 1978) it was found that for no ethylene oxide in the feed stream and for low conversions (<25%) r, was small enough to be neglected. In the present experiments, excess ethylene oxide was introduced in the feed and therefore the assumption OETo30 cannot be valid. A satisfactory kinetic model for ethylene oxidation under these conditions should account not only for the kinetics (Figures 3, 4), but also for the surface oxygen activity behavior (Figure 5). Furthermore, it should not contradict the results previously reported (Stoukides and Vayenas, 1980, 1981). Along these lines and assuming thermodynamic equilibrium between surface and gaseous ethylene as well as between surface and gaseous ethylene oxide one may write:


Using Eqs. (21) and (22) we could modify Eqs. (7), (8), and (9) as follows:



where the values of K , , K,, K,, KETo and K , are the same as those shown in Eqs. (10) through (14). In presence of excess ethylene oxide the rates rco, and rETo can be written as: rco, = rz and

+ r3 =

+K P3 K ~E T~ O(PET0)2 1 + KETPET + KETO(~'ETO),

2 K ~ ~

FIGURE 9 Predicted rates of ethylene oxide formation, ethylene oxide oxidation and ethylene deep , = 0.0105 bar. Po, = 0.1 bar. oxidation at 400C. P


FIGURE 10 Predicted rates o f ethylene oxide formation, ethylene oxide oxidation and ethylene deep oxidation at 280C. P,, = 0.01 15 bar, Po, = 0 . l bar.

The values of r,, r,, r,, r,,, and rco, predicted from Eqs. (7a), (8a), (9a), (23), and and (24) are shown in Figures 9 and 10 for 400" and 280" respectively. The experimentally observed rates rETo and r o , are also shown. A reasonable agreement between experimental and predicted values for r o , and rETo is observed. In addition to the kinetic results the behavior of a, should be in agreement with that predicted by the model. Assuming that the measured open-circuit EMF reflects the activity of atomically adsorbed oxygen rather than any other type of oxygen species present on the catalyst surface one can write a steady state material balance for atomic oxygen: ~ ~ ( P o , ) ' ~~ (l( - 1 ~E T

-~ETO -) ~ , e , ( l - ~ E T~ETO) -Y K ~ ~ E +T K ~I O ~ E T-~KO ~~ ~ O ~= E 0 T (25) O



Justification of the form of adsorption, desorption and reaction terms has been presented in detail in a previous communication (Stoukides and Vayenas, 1981). The only term added in the present case is the last one "-K3808,0" to account for the non-negligible rate of ethylene oxide oxidation to C o t . Dividing all terms of Eq. (25) by KA(l - Oo)(l - eET - OETO)and taking into account Eqs. (21) and (22) and also (Stoukides and Vayenas, 1981) that:

one obtains

Equation (27) implies that for constant PET and Po, the term (Po,)lnao should be proportional to (pETo)'. Indeed, in Figure 11, where the experimental data are plotted as P&:la, vs. (pETo)', a linear dependence is observed for all temperatures examined. Although the above presented analysis does not prove that the interpretation given is a unique one to explain the experimental observations, it provides reasonable and quantitative agreement with both kinetic and potentiometric measurements. According then to the above model the main conclusions can be summarized as: a) Most probably ethylene oxide and ethylene compete for the same sites on the catalyst surface. b) In agreement with previous works, r3 is negligible under the usual conditions for ethylene oxidation (excess air, low conversions). However, if PETo increases in the reactor the secondary oxidation of ethylene oxide to complete oxidation products may become important and consequently the reaction selectivity drops considerably. The results in the range of flowrates where the external transfer limitations are significant are an indirect verification of the fact that the reaction of ethylene combustion r2 has a higher activation energy than the reaction of ethylene epoxidation r,. It can be seen from Eqs. (7a) and (8a) that the dependence of both r, and r2 on the gas phase composition is the same, so the selectivity is a function of the temperature only. Thus, the temperature gradient which is formed between the bulk and the catalyst surface is responsible for the change in the selectivity. Since both reactions are exothermic, the temperature on the catalyst surface is higher than the one in the bulk and increases as the flowrate decreases. Hence, since the activation energy of complete oxidation is higher than the activation energy of epoxidation, the selectivity drops. The data in Table I1 can be used to calculate the mass and heat transfer coefficients from the following


FIGURE 1 1 Dependence of surface oxygen activity on gas composition. P,,=0.0105 0. I bar.

bar, Po,=

mass and heat balance equations:

r, AH, + r, AH, = hA(Tb - T,)


The subscripts "b" and "s" refer to values in the bulk and right above the surface respectively. Of course, the mass and heat transfer coefficients increase with the flowrate. If we assume the following dependence of the mass and heat transfer coefficients on the flowrate

we find that the best fit to the data is obtained for C, = 1.78 X

q t = 1.98,


Predicted values in the range of external transfer limitations

C, = 3.41 x lo-' and q2 = 1.96 when Q is expressed in cm3/min, K,A is in m3/s and hA is in calls. K. Namely, it is found that both the mass and the heat transfer coefficients are proportional to the square of the flowrate. The predicted values of rl, r2 and S using the above expressions for K,A and hA are shown in Table 111. Comparing these values with the ones obtained experimentally we may observe that in some cases there is a good agreement between the experimental and the predicted values while in other cases the agreement is not so good. This may be due to a more complicated dependence of the mass and heat transfer coefficient, on the flowrate than the one expressed by Eqs. (30,31). Nevertheless, Eqs. (30,31) can be used as approximations to derive qualitative conclusions on the effect of external transfer limitations on the performance of the system. Figures 12 and 13 show the reaction rates r, and r,, the selectivity S and the temperature of the catalyst surface T, as functions of the flowrate Q. Equations (28,29) and (30,31) were used for computing these curves with the partial pressure of ethylene in the bulk being PET,, =6 x bar. It can be seen that as the flowrate decreases, the reaction rate rl decreases while r2 initially increases, goes through a maximum and then decreases. The temperature on the surface of the catalyst increases as the flowrate decreases and this causes the initial increase of r2, but the partial pressure of ethylene near the surface of the catalyst decreases and this results to decrease of r, and r2 at low flowrates. The selectivity S decreases at low flowrates because of increase of the temperature on the catalyst surface.


FIGURE 12 Predicted values of reaction rates r,, r, in presence of significant diffusion limitations.

FIGURE 13 Effect of diffusion limitations on catalyst temperature and reaction selectiv~ty.



Besides the temperature gradient formed between the bulk and the catalyst surface, one could think of some other phenomena that could contribute to the drop in the selectivity with decreasing flowrate. First of all, the approximations in Eqs. (17,18) are not necessarily valid in the range of strong diffusion limitations. T o that end, the rate of ethylene oxide oxidation r3 was measured independently by introducing air and ethylene oxide in the reactor at flowrates and partial pressures of ethylene oxide similar to those shown in Table 11. The values of r, found were again two orders of magnitude lower than those of r, and r2 under the same flowrate conditions. Thus, the decrease in S shown in Figure 8 cannot be attributed to a relative increase in r, in the region of low flowrates. Also at low flowrates the gas phase mixing in the reactor might be incomplete and the assumption of CSTR behavior may no longer hold. This could contribute to the decrease in r, and r2. Using the infrared C 0 2 analyzer (Stoukides and Vayenas, 1980) we obtained the residence time distribution function over the flowrate range of 40-300cm3/min. It was found that even for the lowest flowrate used, the reactor behavior was very close ( < 5 % deviation) to that of the CSTR. Thus, the observed phenomena could not be attributed to deviation from ideal CSTR behavior. Another phenomenon that could contribute to the drop of the selectivity with decrease of the flowrate is the inhibiting effect that C 0 2 has on the rate of ethylene epoxidation r, as reported by Stoukides and Vayenas (1981). As the flowrate decreases, the reaction conversion increases and thus the C 0 2 concentration in the reactor increases. Moreover, the diffusion rate between the catalyst surface and the bulk decreases upon decreasing the flowrate. This causes a further increase of the C 0 2 concentration near the catalyst surface. Due to the inhibiting effect of C 0 2 on r,, the selectivity is expected to decrease. However, the inhibiting effect of C 0 2 becomes important at lower temperatures and is of minor significance at temperatures greater than 400C. This implies that the inhibiting effect of C 0 2 contributes very little to the decrease in the selectivity. Therefore, we may conclude that the external temperature gradient is mainly responsible for the observed drop in the selectivity with decrease of the flowrate. An internal temperature gradient may also have some effect in the present case, but as it has been stressed in various analyses (Carberry, 1975; Hutchings and Carberry, 1966) and experimental observations (Butt et al., 1977; Kehoe and Butt, 1972) for gas-solid catalytic reactions, the predominant temperature gradient occurs in the external film and the catalyst itself may be taken as internally isothermal. Also, the pore size of the Ag catalyst used in the present study was quite large 1 pm) and internal diffusion was found to be negligible (Stoukides and Vayenas, 1980, 1981). In conclusion, the present work shows that the observed phenomenon of considerable decrease in the selectivity in the regime of low flowrates can be mainly attributed to the difference in activation energies of the two reactions r, and r2 and to the temperature gradient that is formed between the bulk and the catalyst surface. The inhibiting effect of C 0 2 on r , and temperature gradients inside the catalyst pores may also contribute to the selectivity drop to a minor extent. Due to the industrial importance of ethylene oxide production from
( 2



ethylene, it is highly desirable to minimize the production of COz, i.e. maximize the selectivity. Presence of external mass and heat transfer limitations causes a substantial decrease in selectivity. Therefore, care should be taken to operate the reactor in the range of conditions where external transport phenomena are not important. NOMENCLATURE Surface oxygen activity Mass and heat transfer area, m2 Electromotive force, volts Faraday's constant, 96,500 Cb gr equivalent-' Total molar flowrate, molels Heat transfer coefficient, cal s-' K-' m-2 Mass transfer coefficient, m .s-' Kinetic rate constants, mole . s-' Adsorption coefficients for ethylene and ethylene oxide respectively Adsorption and desorption rate constants for atomic oxygen Adsorption coefficient for atomic oxygen Partial pressure of species i, bar Volumetric flowrate, cm31min Rate of reactions of ethylene epoxidation (i = I), ethylene deep oxidation (i = 2) and ethylene-oxide oxidation (i = 3) Ideal gas constant, 1.987 cal mole-' K-' Selectivity to ethylene oxide (moles of ethylene oxide produced per mole of ethylene consumed) Absolute temperature, K

Greek Symbols
dimensionless coefficient, y(KzIKl)Z 1 (Stoukides and Vayenas, 1981) PET,i-PET i.e. inlet minus outlet partial pressure of ethylene in the reactor coverage of species i chemical potential of oxygen standard chemical potential of oxygen in gas phase






We gratefully acknowledge the National Science Foundation for financial support through NSF Grant CPE 82-15085.We also thank Prof. C.G. Vayenas for his useful comments on this work.

REFERENCES 1. Barteau, M.A., and Madix, R.J., "The Chemical Physics of Solid Surfaces and Hererogeneour Catalysis", D.A. King and D.P. Woodruff, Editors. Vol. 4, (1982). 2. Butt, J.B., Downing, D.M., and Lee, J.W., "Inter-Intraphase Temperature Gradients in Fresh and Deactivated Catalyst Particles", Ind. Eng. Chem. Fund., 16, 270 (1977). 3. Campbell, C.T., and Paffett, M.T., "Model Studies of Ethylene Epoxidation Catalyzed by the Ag.(llO) Surface", Surf Sci. 139,396 (1984). 4. Cant, N.W., and Hall, W.K., "Oxidation of Labeled Olefins over Silver", I . Catal. 52, 81 (1978). 5. Carberry, J.J., Kuczynski, G.C., and Martinez, E., "On the Influence of y-Irradiation upon Catalytic Selectivity". I. Catal. 26, 247 (1972). 6. Carberry, J.J., "On the Relative Importance of External-Internal Temperature Gradients in Heterogeneous Catalysis", Ind. Eng. Chem. Fund. 14, 129 (1975). 7. Etsell, T.H., and Flengas, S.N., "Overpotential Behavior of Stabilized Zirconia Solid Electrolyte Fuel Cells", I. Electrochem. Soc. 118(12), 1890 (1971). 8. Force, E.L., and Bell, A.T., "The Relationship of Adsorbed Species Observed by Infrared Spectroscopy to the Mechanism of Ethylene Oxidation over Silver", I. Catal. 40, 356 (1975). 9. Ghazali, S., Park, D.W., and Gau, G., "Kinetics of Ethylene Epoxidation on a Silver Catalyst", Appl. Caral. 6, 195 (1983). 10. Grant, R.B., and Lambert, R.M., (i) "Ethylene Oxide Isomerization on Single-Crystal Ag. (111) in Atomically Clean and Cs-Moderated Conditions", I. Catal. 93, 32 (1985). (ii) "A Single Cwstal Studv of the Silver-Catalned Selective Oxidation and Total Oxidation of Ethvlene", I. c i a / . 92, 381 (1985). 11. Giir, T.M., and Huggins, R.A., "Electrocatalytic Synthesis of Methane on Stabilized Zirconia from H X O , Mixtures". Solid Slate lonics 5. 563 (1981). 12. Harriot, P., "The oxidation of Ethylene using h w b n Different Supports", I. Caral. 21, 56 (1971). 13. Haul, R., Neubauer, G., Fischer, D., Hoge, D., and Zeeck, U., "Kinetic and TDS Studies on the Silver Catalyzed Ethene Oxidation", Proc. Int. Congress on Catalysis, Berlin, Vol. 111, 265 (1984). 14. Hayes, K.E., "The Role of Reaction Products in the Silver Catalyzed Oxidation of Ethylene", Can. I . Chem. 38, 2256 (1960). 15. Hutchings. J. and Carberry, J.J., "The Influence of Surface Coverage on Catalytic Effectiveness 20 (1966). and Selectivity. The Isothermal and Nonisothermal Cases", AIChE lournal U, 16. Johnson, D.L., and Verykios, X.E., "Selectivity Enhancement in Ethylene Oxidation Employing Partially Impregnated Catalysts", I. Catal. 79, 156 (1983). 17. Kehoe, J.P.G., and Butt, J.B., "lnteractions of Inter- and Intraphase Gradients in a Diffusion Limited Catalytic Reaction", AIChE lournal 18, 347 (1972). 18. Kilty, P.A., and Sachtler, W.M.H., "The Mechanism of the Selective Oxidation of Ethylene to Ethylene Oxide", Cat. Rev.-Sci. Eng. 10, 1 (1974). 19. Kilty, P.A., Rol, N.C.. and Sachtler, W.M.H., "Identification of Oxygen Complexes Adsorbed on Silver and their function in the Catalytic Oxidation of Ethylene", 5th Int. Congress on Catalysis, Miami, Paper 64 (1972). 20. Kummer, J.T., "The Catalytic Oxidation of Ethylene to Ethylene Oxide Over Single Crystals of Silver", I. Phys. Chem. 60, 666 (1956). 21. Ostrovskii, V.E., Kulkova, N.V., Lopatin, V.L.. and Temkin, M.I., "The Modifying Action of Additives to the Ethylene Oxidation Catalyst", Kiner. Karol. 3, 183 (1962). 22. Pancharatnam, S., Huggins, R.A., and Mason, D.M., "Catalytic Decomposition of Nitric Oxide 869 (1975). on Zirconia by Electrolytic Removal of Oxygen", I. Elecrroch. Soc. U2, 23. Sachtler, W.M.H., Backx, C., and Van Santen, R.A., "On the Mechanism of Ethylene Epoxidation", Car. Rev.-Sci. Eng. 23, 127 (1981).



24. Stoukides, M., and Vayenas, C.G., "Solid Electrolyte Aided Study of the Ethylene Oxide Oxidation on Silver", I. Catal. 64, 18 (1980). 25. Stoukides, M., and Vayenas, C.G., "Solid Electrolyte Aided Study of the Ethylene Oxidation on Polycrystalline Silver", I. Carol. 69, 18 (1981). 26. Temkin, M.I., "Oxidation of Ethylene into Ethylene Oxide", Adu. Car. 28, 230 (1979). 27. Vayenas, C.G., Georgakis, C., Michaels, J., and Tormo, J., "The Role of Pro, in the Isothermal Rate Oscillations of Ethylene Oxidation on Platinum", I. Carol. 67, 348 (1981). 28. Vayenas, C.G., and Farr, R.D., "Cogeneration of Electric Energy and Nitric Oxide", Science 208, 533 (1980). 29. Voge, H.H., and Adams, C.R., "Catalytic Oxidation of Olefins", Adu. Caral. 17, 154 (1967). 30. Wachs, I.E., and Kelemen, S.R., "The Interactions of Ethylene and Ethylene Oxide with Surface Carbonate and Hydroxide Intermediates on Silver", I . Carol. 68, 213 (1981). 31. Wagner, C., "Adsorbed Atomic Species as Intermediates in Heterogeneous Catalysis", Adu. Carol. 21, 323 (1970).