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NASA NTRS1992

The role of specular reflectance in surface anisotropy

For smooth surfaces, specular reflection constitutes a major source of anisotropy in the surface bidirectional reflectance and introduces a strong illumination angle dependence in diurnal albedo. A prior formulation has been employed by the authors to account for the surface anisotropy of other natural surfaces. It is shown that this formulation is appropriate to successfully explain the specular characteristics of other rough surfaces as well as that of the ocean. The angular dependence of the diffuse component of the reflected radiance is explained using the Ahmad-Deering formulation, which is based on Chandrasekhar's radiative transfer solution. Results for a smooth silt-playa lake bed in a volcanic region of Nevada are presented. It is shown that this formulation is capable of explaining the specular features measured in the field and can be effectively used in any surface bidirectional reflectance model.

Ahmad, Suraiya P.↗
NASA NTRS1993

Porosity and the ecology of icy satellites

The case for a significant role for porosity in the structure and evolution of icy bodies in the Solar System has been difficult to establish. We present a relevant new data set and a series of structure models including a mechanical compression, not thermal creep, model for porosity that accounts satisfactorily for observed densities, moments of inertia, geologic activity, and sizes of tectonic features on icy satellites. Several types of observational data sets have been used to infer significant porosity, but until recently, alternative explanations have been preferred. Our first area of concern is the occurrence of cryovolcanism as a function of satellite radius; simple radiogenic heating models of icy satellites suggest minimum radii for melting and surface cryovolcanism to be 400 to 500 km, yet inferred melt deposits are seen on satellites half that size. One possible explanation is a deep, low conductivity regolith which lowers conductivity and raises internal temperatures, but other possibilities include tidal heating or crustal compositions of low conductivity. Our second area of concern is the occurrence and magnitude of tectonic strain; tectonic structures have been seen on icy satellites as small as Mimas and Proteus. The structures are almost exclusively extensional, with only a few possible compression Al features, and inferred global strains are on the order of 1 percent expansion. Expansions of this order in small bodies like Mimas and prevention of late compressional tectonics due to formation of ice mantles in larger bodies like Rhea are attained only in structure models including low-conductivity, and thus possibly high porosity, crusts. Thirdly, inferred moments of inertia less than 0.4 in Mimas and Tethys can be explained by high-porosity crusts, but also by differentiation of a high density core. Finally, the relatively low densities of smaller satellites like Mimas and Miranda relative to larger neighbors can be explained by deep porosity, but also by bulk compositional differences. Recent work has strengthened the case for significant porosity. Halley's nucleus was found to have a density near 0.6 g/cu cm, Janus and Epimethus were proposed to have densities near 0.7 g/cu cm, densities almost certainly due to high porosity. The irregular-spherical shape transition of icy satellites was quantitatively explained by low conductivity regoliths. A creative structure/thermal history model for Mimas simultaneously accounts quantitatively for Mimas' low density and moment of inertia by invoking initial high-porosity and subsequent compaction in the deep interior by thermal creep. The main problem with this promising model is that approximately 7 percent predicts a reduction in Mimas' radius, implying significant compressional failure and prevention of extensional tectonics, in contradiction to the observed extensional features and inferred 1 percent expansion in radius.

Croft, Steven K.↗
NASA NTRS1993

Magnetic fields and nonuniform structures of the Moon

Direct magnetic measurements performed by space probes demonstrated the existence of small-scale, stationary surface magnetic fields on the Moon. The magnetic field averaged over a region of approximately 600 km was found to be no larger than approximately 10(exp -5) G, that of the regions approximately 100-200 km is approximately 10(exp -5) to 10(exp -4) G, and that of approximately 10-100 km reaches approximately 10(exp -3) G. Investigations of certain lunar rocks reveal stable residual magnetization, which could have been acquired during the crystallization of the rocks in the presence of the outer magnetic field, provided such a field existed at the initial stage of lunar evolution. Estimates show that 4 x 10(exp 9) yr ago the field was small, then it rose to approximately 1.3 G at the beginning of 3.9 x 10(exp 9) yr with a subsequent exponential decrease during the period of 3.9 x 10(exp 9) yr to 3.2 x 10(exp 9) yr ago. Small-scale fields have been explained by some authors as due to mechanical impacts produced by meteors. The theory of this effect is not elaborated in detail. This can in no way explain the paleomagnetic data. These data are commonly explained as a result of the dynamo action in the liquid lunar core.

Dolginov, A. Z.↗
NASA NTRS1993

Transmantle flux tectonics

Venus, Earth, and Mars have surfaces that display topographic domes and depressions with quasi-circular planimetric shapes, relief of 0 to several km, and large spatial scales (10(exp 2) to 10(exp 4) km). Our morphostructural mapping reveals hierarchical arrangements of these features. They are explained by a model of long-acting mantle convection, as a particular case of convection in a stratified and random inhomogeneous medium, which develops the form of a hierarchy of different convective pattern scales, each arising from different levels in the mantle. The hypothesis of transmantle flux tectonics parsimoniously explains a diversity of seemingly unrelated terrestrial planetary phenomena, including Earth megaplumes, global resurfacing epochs on Venus, and cyclic ocean formation and global climate change for Mars. All these phenomenon are hypothesized to be parsimoniously explained by a process of transmantle flux tectonics in which long-acting mantle convection generates stresses in blocks of planetary lithosphere to produce distinctive quasi-circular global-hierarchical morphostructure (QGM) patterns. Transmantle flux tectonics differs from plume tectonics in that individual plumes are not considered in isolation. Rather, a wholly interactive process is envisioned in which various spatial and temporal scales of convection operate contemporaneously and hierarchically within other scales. This process of continual change by hierarchical convective cells affects the surface at varying temporal and spatial scales, and its effects are discernable through their relic geological manifestations, the QGM patterns.

Finn, V. J.↗
NASA NTRS1993

Two populations and models of gamma ray bursts

Gamma-ray burst statistics are best explained by a source population at cosmological distances, while spectroscopy and intensity histories of some individual bursts imply an origin on Galactic neutron stars. To resolve this inconsistency I suggest the presence of two populations, one at cosmological distances and the other Galactic. I build on ideas of Shemi and Piran (1990) and of Rees and Mesozaros (1992) involving the interaction of fireball debris with surrounding clouds to explain the observed intensity histories in bursts at cosmological distances. The distances to the Galactic population are undetermined because they are too few to affect the statistics of intensity and direction; I explain them as resulting from magnetic reconnection in neutron star magnetospheres. An appendix describes the late evolution of the debris as a relativistic blast wave.

Katz, J. I.↗
NASA NTRS1993

Carbonates, surfates, phosphates, nitrates, and organic materials: Their association in a Martian meteorite

The debate concerning the evolution of CO2 on Mars continues. It would appear that in order to explain the valley networks and other relict fluvial landforms it is necessary to accept that liquid water was once present at the surface of Mars. This in turn requires, at some point in the planet's history, a higher surface temperature than exists today, proposition explained traditionally by an early dense CO2, atmosphere. However, there are a number of problems with this notion: for instance, CO2 alone is not an efficient greenhouse gas because of its tendency to form clouds. Moreover, if there was an early dense CO2 atmosphere, it is necessary to explain where the elemental constituents now reside. There are two possibilities for the latter, namely loss to outer space of atmospheric CO2 or the formation of vast carbonate deposits. While some models of atmospheric loss predict that up to 0.4 bar of CO2 could be removed from the Martian surface, this is still not enough to account for the original atmospheric inventory, usually considered to have been in the range of 1-5 bar. Thus, most models of the evolution of the Martian surface require removal of CO2 from the atmosphere and into carbonate deposits. However, as yet, the evidence for the existence of carbonates on Mars is fairly scant. This is an issue that would have been resolved by results obtained from Mars Observer.

Wright, I. P.↗
NASA NTRS1994

Formation of fold and thrust belts on Venus due to horizontal shortening of a laterally heterogeneous lithosphere

An outstanding question relevant to understanding the tectonics of Venus is the mechanism of formation of fold and thrust belts, such as the mountain belts that surround Lakshmi Planum in western Ishtar Terra. These structures are typically long (hundreds of km) and narrow (many tens of km), and are often located at the margins of relatively high (km-scale) topographic rises. Previous studies have attempted to explain fold and thrust belts in various areas of Venus in the context of viscous and brittle wedge theory. However, while wedge theory can explain the change in elevation from the rise to the adjacent lowland, it fails to account for a fundamental aspect of the deformation, i.e., the topographic high at the edge of the rise. In this study we quantitatively explore the hypothesis that fold and thrust belt morphology on Venus can alternatively be explained by horizontal shortening of a lithosphere that is laterally heterogeneous, due either to a change in thickness of the lithosphere or the crust. Lateral heterogeneities in lithosphere structure may arise in response to thermal thinning or extensive faulting, while variations in crustal thickness may arise due to either spatially variable melting of mantle material or by horizontal shortening of the crust. In a variable thickness lithosphere or crust that is horizontally shortened, deformation will tend to localize in the vicinity of thickness heterogeneity, resulting in a higher component of dynamic topography there as compared to elsewhere in the shortening lithosphere. This mechanism may thus provide a simple explanation for the topographic high at the edge of the rise.

Zuber, M. T.↗
NASA NTRS1993

Master plot analysis of microcracking in graphite/epoxy and graphite/PEEK laminates

We used a variational stress analysis and an energy release rate failure criterion to construct a master plot analysis of matrix microcracking. In the master plot, the results for all laminates of a single material are predicted to fall on a single line whose slope gives the microcracking toughness of the material. Experimental results from 18 different layups of AS4/3501-6 laminates show that the master plot analysis can explain all observations. In particular, it can explain the differences between microcracking of central 90 deg plies and of free-surface 90 deg plies. Experimental results from two different AS4/PEEK laminates tested at different temperatures can be explained by a modified master plot that accounts for changes in the residual thermal stresses. Finally, we constructed similar master plot analyses for previous literature microcracking models. All microcracking theories that ignore the thickness dependence of the stresses gave poor results.

Nairn, John A.↗
NASA NTRS1995

SeaWiFS Technical Report Series. Volume 29: SeaWiFS CZCS-type pigment algorithm

The Sea-viewing Wide Field-of-view Sensor (SeaWiFS) mission will provide operational ocean color that will be superior to the previous Coastal Zone Color Sensor (CZCS) proof-of-concept mission. an algorithm is needed that exploits the full functionality of SeaWiFS whilst remaining compatible in concept with algorithms used for the CZCS. This document describes the theoretical rationale of radiance band-radio methods for determining chlorophyll alpha and other important biogeochemical parameters, and their implementation for the SeaWiFS mission. Pigment interrelationships are examined to explain the success of the CZCS algorithms. In the context where chlorophyll alpha absorbs only weakly at 520 nm, the success of the 520 nm to 550 nm CZCS band ratio needs to be explained. This is explained by showing that in pigment data from a range of oceanic provinces chlorophyll alpha (absorbing at less than 490 nm), carotenoids (absorbing at greater than 460 nm), and total pigment are highly correlated. Correlations within pigment groups particularly photoprotectant and photosynthetic carotenoids are less robust. The sources of variability in optical data re examined using the NIMBUS Experiment Team (NET) bio-optical data set and bio-optical model. In both the model and NET data, the majority of the variance in the optical data is attributed to variability in pigment (chlorophyll alpha, and total particulates, with less than 5% of the variability resulting from pigment assemblage. The relationships between band ratios and chlorophyll is examined analytically, and a new formulation based on a dual hyperbolic model is suggested which gives a better calibration curve than the conventional log-log linear regression fit. The new calibration curve shows that 490:555 ratio is the best single-band ratio and is the recommended CZCS-type pigment algorithm. Using both the model and NET data, a number of multiband algorithms are developed; the best of which is an algorithm based on the 443:555 and 490:555 ratios. From model data, the form of potential algorithms for other products, such as total particulates and dissolved organic matter (DOM), are suggested.

Hooker, Stanford B.↗
NASA NTRS1994

Asymptotic Giant Branch stars as a source of short-lived radioactive nuclei in the solar nebula

We carried out a theoretical evaluation of the contribution of Asymptotic Giant Branch (AGB) stars to some short-lived (10(exp 6) less than or equal to Tau-bar less than or equal to 2 x 10(exp 7) yr) isotopes in the Interstellar Medium (ISM) and in the early solar system using stellar model calculations for thermally pulsing evolutionary phases of low-mass stars. The yields of s-process nuclei in the convective He-shell for different neutron exposures tau(sub 0) were obtained, and AGB stars were shown to produce several radioactive nuclei (especially Pd-107, Pb-205, Fe-60, Zr-93, Tc-99, Cs-135, and Hf-182) in diferent amounts. Assuming either contamination of the solar nebula from a single AGB star or models for continuous injection and mixing from many stars into the ISM, we calculate the ratios of radioactive to stable nuclei at the epoch of the Sun's formation. The dilution factor between the AGB ejecta and the early solar system matter is obtained by matching the observed Pd-107/Pd-108 and depends on the value of tau(sub 0). It is found that small masses M(sub He) of He-shell material (10(exp -4)-10(exp -7) solar mass) enriched in s-process nuclei are sufficient to contaminate 1 solar mass of the ISM to produce the Pd-107 found in the early solar system. Predictions are made for all of the other radioactive isotopes. The optimal model to explain several observed radioactive species at different states of the proto-solar nebula involves a single AGB star with a low neutron exposure (tau(sub 0) = 0.03 mbarn(sup -1)) which contaminated the cloud with a dilution factor of M(sub He)/solar mass approximately 1.5 x 10(exp -4). This will also contribute newly synthesized stable s-process nuclei in the amount of approximately 10(exp -4) of their abundances already present in the proto-solar cloud. Variations in the degree of homogenization (approximately 30%) of the injected material may account for some of the small general isotopic anomalies found in meteorites. It is also found that Fe-60 is produced in small but significant quantities that may be sufficient to explain the observations if the time elapsed delta from the contamination of the ISM to the formation of protoplanetary bodies is not higher than delta = 5 x 10(exp 6) yr. If delta is longer, up to 10 x 10(exp 6) yr, this would require the single AGB star to experience enhanced neutron densities (n(sub n) approximately 3 x 10(exp 9)n/cu cm) in the s-processing zone in order to compensate for the branching at Fe-59. The alternative model of long-term continuous ejection of matter from many AGB stars does not appear to match the observations. We also estimate the Al-26 production from the H-shell and find that the Al-26 abundance in the early solar system may be readily explained in a self-consistent manner. Moreover, Al-26 from AGB stars may contribute substantially to the galactic Al-26 gamma-source, while no significant gamma-flux from Co-60 (deriving from Fe-60 decay) is to be expected.

Wasserburg, G. J.↗
NASA NTRS1994

Four cells or two? Are four convection cells really necessary?

This paper addresses the question whether a four-cell convection pattern in the polar cap ionosphere is required by observations, or whether the data are fully explainable by a (perhaps highly distorted) two-cell convection pattern. We present convection data from Atmosphere Explorer C, which, if only the flow component in the sunward-antisunward direction were measured, could be explained either as one of two possible distorted two-cell patterns or as a full four-cell pattern. However, neither of the distorted two-cell patterns that are consistent with the sunward-antisunward flow component can be made consistent with the dawn-dusk flow component over the entire spacecraft trajectory, without postulating a severe flow kink and extra field-aligned currents sunward of the spacecraft track. In addition, the zero potential point (which in a four-cell model would mark the division between the two reverse convection cells) also exactly corresponded to the location of the reversal of the east-west component in the flow, a feature predicted from the four-cell model but more difficult to explain in a distorted two-cell model. Because the pattern was repeated on two consecutive passes, time variations can probably be ruled out as a cause of the sunward flow. Between the two northern hemisphere dayside passes, a southern hemisphere nightside pass also showed a region of sunward flow in the polar cap. The fact that in this case the sunward flow was not confined to the dayside also favors a four-cell explanation.

Reiff, P. H.↗
NASA NTRS1994

Two populations and models of gamma-ray bursts

Gamma-ray burst statistics are best explained by a source population at cosmological distances, while spectroscopy and intensity histories of some individual bursts imply an origin on Galactic neutron stars. To resolve this inconsistency I suggest the presence of two populations, one at cosmological distances and the other Galactic. I build on ideas of Shemi & Piran (1990) and of Rees & Meszaros (1992) involving the interaction of fireball debris with surrounding clouds to explain the observed intensity histories in burst at cosmological distances. The distances to the Galactic population are undetermined because they are two few to affect the statistics of intensity and direction; I explain them as resulting from magnetic reconnection in neutron star magnetospheres. An appendix describes the late evolution of the debris as a relativistic blast wave.

Katz, J. I.↗
NASA NTRS1994

The very soft X-ray emission of X-ray-faint early-type galaxies

A recent reanaylsis of Einstein data, and new ROSAT observations, have revealed the presence of at least two components in the X-ray spectra of X-ray faint early-type galaxies: a relatively hard component (kT greater than 1.5 keV), and a very soft component (kT approximately 0.2-0.3 keV). In this paper we address the problem of the nature of the very soft component and whether it can be due to a hot interstellar medium (ISM), or is most likely originated by the collective emission of very soft stellar sources. To this purpose, hydrodynamical evolutionary sequences for the secular behavior of gas flows in ellipticals have been performed, varying the Type Ia supernovae rate of explosion, and the dark matter amount and distribution. The results are compared with the observational X-ray data: the average Einstein spectrum for six X-ray faint early-type galaxies (among which are NGC 4365 and NGC 4697), and the spectrum obtained by the ROSAT pointed observation of NGC 4365. The very soft component could be entirely explained with a hot ISM only in galaxies such as NGC 4697, i.e., when the depth of the potential well-on which the average ISM temperature strongly depends-is quite shallow; in NGC 4365 a diffuse hot ISM would have a temperature larger than that of the very soft component, because of the deeper potential well. So, in NGC 4365 the softest contribution to the X-ray emission comes certainly from stellar sources. As stellar soft X-ray emitters, we consider late-type stellar coronae, supersoft sources such as those discovered by ROSAT in the Magellanic Clouds and M31, and RS CVn systems. All these candidates can be substantial contributors to the very soft emission, though none of them, taken separately, plausibly accounts entirely for its properties. We finally present a model for the X-ray emission of NGC 4365, to reproduce in detail the results of the ROSAT pointed observation, including the Position Sensitive Proportional Counter (PSPC) spectrum and radial surface brightness distribution. The present data may suggest that the X-ray surface brightness is more extended than the optical profile. In this case, a straightforward explanation in terms of stellar sources could not be satisfactory. The available data can be better explained with three different contributions: a very soft component of stellar origin, a hard component from X-ray binaries, and an approximately 0.6 keV hot ISM. The latter can explain the extended X-ray surface brightness profile, if the galaxy has a dark-to-luminous mass ratio of 9, with the dark matter very broadly distributed, and a SN Ia explosive rate of approximately 0.6 the Tammann rate.

Pellegrini, S.↗
NASA NTRS1993

An analysis of nearfield normal mode amplitude anomalies of the Landers earthquake

The 1992 Landers earthquake (M(sub w) = 7.3) occurred in the middle of the TERRAscope network. Long-period Rayleigh waves recorded at the TERRAscope stations (delta less than or = 3 deg) after traveling around the Earth show large amplitude anomalies, one order of magnitude larger than spherical Earth predictions up to a period of about 600 s. The ground motions over the epicentral region at and after the arrival of R4-5 are in phase at all stations. These observations are inconsistent with the nearly vertical strike slip mechanism of the Landers earthquake. Synthetic seismograms for a rotating, elliptic, and laterally heterogeneous Earth model calculated by the variational method agree well with the observed waveforms. Calculations for various 3D Earth models demonstrate that the amplitudes are very sensitive to the large scale aspherical structure in the crust and the mantle. The anomalies for modes shorter than 300 s period can be explained by lateral heterogeneity shallower than the upper mantle. Rotation of the Earth and lower mantle heterogeneity are required to explain mode amplitudes at longer periods. Current whole mantle seismic tomographic models can fully explain the observed amplitudes longer than 300 s. To assess the effect of the high order lateral heterogeneity in the mantle more precise estimate of the crustal correction is required.

Watada, Shingo↗
NASA NTRS1994

Monoterpene emission from ponderosa pine

We explore the variability in monoterpene emissions from ponderosa pine beyond that which can be explained by temperature alone. Specifically, we examine the roles that photosynthesis and needle monoterpene concentrations play in controlling emissions. We measure monoterpene concentrations and emissions, photosynthesis, temperature, and light availability in the late spring and late summer in a ponderosa pine forest in central Oregon. We use a combination of measurements from cuvettes and Teflon bag enclosures to show that photosynthesis is not correlated with emissions in the short term. We also show that needle monoterpene concentrations are highly correlated with emissions for two compounds, alpha-pinene and beta-pinene, but that Delta-carene concentrations are not correlated with emissions. We suggest that direct effects of light and photosynthesis do not need to be included in emission algorithms. Our results indicate that the role of needle concentration bears further investigation; our results for alpha-pinene and beta-pinene are explainable by a Raoult's law relationship, but we cannot yet explain the cause of our results with Delta-carene.

Lerdau, Manual↗
NASA NTRS1994

Historical photometric evidence for volatile migration on Triton

Analysis of CCD images of Triton obtained with the 1.5-m telescope on Palomar Mountain shows that in the time period surrounding the Voyager 2 encounter with the satellite (1985-1990), no changes in the satellite's visual albedo or color occurred. The published observations of Triton in the 0.35- to 0.60-micrometer spectral region obtained between 1950 and 1990 were reanalyzed to detect historical variability in both its albedo and visual color. Analysis of the photometry indicates that there is little, if any, change in Triton's visual geometric albedo. This result is consistent with the albedo pattern observed by Voyager and the change in sub-Earth latitude. Two distinct types of color changes are evident: a significant secular increase in the blue region of the visual spectrum since at least the 1950s, and the reported dramatic reddening of Triton's spectrum in the late 1970s. The latter change can be explained only by a short-lived geological phenomenon. Triton's changing pole orientation with respect to a terrestrial observer cannot explain the secular color changes. These changes imply volatile transport on a global scale on Triton's surface during the past 4 decades. We present two models which show that either removal of a red volatile from Triton's polar cap or deposition of a blue volatile in the equatorial regions can explain the secular color changes. A third possibility is that the changes are the result of the alpha-beta phase transition of nitrogen and subsequent fracturing of the polar cap region (N. S. Duxbury and R. H. Brown (1993).

Buratti, Bonnie J.↗
NASA NTRS1994

Venus' center of figure-center of mass offset

Magellan altimetry data reveal that the center of figure (CF) of Venus is displaced approximately 280 m from its center of mass (CM) toward 4.4 deg S, 135.8 deg E, a location in Aphrodite Terra. This offset is smaller than those of other terrestrial planets but larger than the estimated error, which is no more than a few tens of meters. We examine the possibility that the CF-CM offset is related to specific geologic provinces on Venus by deriving three simple models for the offset: a thick-crust model, a hotspot model, and a thick-lithosphere model. The offset caused by a region of thick crust depends upon the region's extent, the crust-mantle density contrast, and the thickness of excess crust. A hotspot-related offset depends on the extent of the thermally anomalous region and the magnitude of the thermal anomaly. Offset due to a region of thick lithosphere depends upon the extent of the region, the average temperature contrast across the lithosphere, and the amount of excess lithosphere. We apply the three models to Venus plateau-shaped highlands, volcanic rises, and lowlands, respectively, in an attempt to match the observed CF-CM offset location and magnitude. The influence of most volcanic rises and of Ishtar Terra on the CF-CM offset must be quite small if we are to explain the direction of the observed offset. The lack of influence of volcanic rises can be explained if the related thermal anomalies are limited to a few hundred degrees or less and are plume-shaped (i.e., characterized by a flattened sublithospheric `head' with a narrow cylindrical feeder `tail'). The unimportance of Ishtar Terra is most easily explained if it lies atop a significant mantle downwelling.

Bindschadler, Duane L.↗
NASA NTRS1995

Supporting technology for the development of Controlled Ecological Life Support Systems (CELSS)

To support the development of Controlled Ecological Life Support Systems (CELSS) in the space program, a metabolic simulator has been selected for use in a closed chamber to test functions of the CELSS. This metabolic simulator is a catalytic reactor which oxidizes the methyl acetate to produce carbon dioxide and water vapor. In this project, kinetic studies of catalytic oxidation of methyl acetate were conducted using monolithic and pellet catalysts with 0.5% (by weight) platinum (Pt) on aluminum oxide (Al2O3). The reaction was studied at a pressure of one atmosphere and at temperatures varying from 160 C to 420 C. By-products were identified at the exit of the preheater and reactor. For the kinetic study with the monolithic catalyst, a linear regression method was used to correlate the kinetic data with zero-order, first-order and Langmuir-Hinshelwood models. Results indicate that the first-order model represents the data adequately at low concentrations of methyl acetate. For higher concentrations of methyl acetate, the Langmuir-Hinshelwood model best represents the kinetic data. Both rate constant and adsorption equilibrium constants were estimated from the regression. A Taguchi orthogonal array (L(sub 9)) was used to investigate the effects of temperature, flow rate, and concentration on the catalytic oxidation of methyl acetate. For the monolithic catalyst, temperature exerts the most significant effect, followed by concentration of methyl acetate. For the pellet catalyst, reaction temperature is the most significant factor, followed by gas flow rate and methyl acetate concentration. Concentrations of either carbon dioxide or oxygen were seen to have insignificant effect on the methyl acetate conversion process. Experimental results indicate that the preheater with glass beads can accomplish thermal cracking and catalytic reaction of methyl acetate to produce acetic acid, methanol, methyl formate, and 1-propanol. The concentration of all by-products was measured in ppmv (parts per million by volume). At higher temperatures, greater amounts of these products are produced, as expected. In all cases, methanol was the predominant concentration detected, followed by methyl formate. At temperatures lower than 320 C for the P-type monolithic catalyst, methanol, acetic acid, and acetone were detected, whereas, for the E-type monolithic catalyst, only methanol was detected at 160 C. Both P and E types of the monolithic catalyst were specified with the same substrates (ceramic), washcoat (Al2O3), and promoter (Pt). However, the manufacturing and treatment procedures were quite different. It was therefore concluded that the performance of the E-type monolithic catalyst is superior to that of the P-type for oxidation of methyl acetate. At higher reaction temperatures, e.g., above 420 C, all reactants and byproducts were completely oxidized using these two types of monolithic catalyst to produce carbon dioxide and water vapor. A complex heterogenous catalytic reaction mechanism was proposed to explain the formation of the byproducts (methanol, acetic acid, and methyl formate) as the methyl acetate traveled through the preheater packed with glass beads. The by-product, 1-propanol, may be formed only through a homogeneous reaction, since it is difficult to develop a reasonable sequence of heterogeneous reaction steps to explain its formation. The homogeneous thermal decomposition of methyl acetate to form free radicals was proposed to explain the formation of 1-propanol, and also methanol, in the preheater. A dual-site catalytic reaction mechanism was proposed for the oxidation of methyl acetate over Pt/Al2O3 monolithic catalyst. The dual-site mechanism describes the chemisorption of oxygen molecules as well as a physical adsorption of methyl acetate on the active sites. On the active sites, methyl acetate is oxidized rapidly to form carbon dioxide and water vapor. A rate equation derived from this mechanism gives the Langmuir-Hinshelwood rate formula which has been observed from the experimental data obtained in this project for high methyl acetate concentration (greater than 1000 ppmv) over a monolithic catalyst. If the oxygen concentration is very high and methyl acetate concentration is very low, the reaction rate equation is then reduced to a first-order with respect to methyl acetate concentration. The first-order model has also been observed from the experimental data obtained in this project for low methyl acetate concentration (less than 1000 ppmv).

Li, Ku-Yen↗