Substrate-inhibited kinetics with catalyst deactivation in an isothermal CSTR. II. Multiple pseudosteady states and reactor failure

Analytical expressions are derived for the time and magnitude of failure of an isothermal CSTR with substrate-inhibited kinetics, caused by slow catalyst deactivation under three types of parallel and series mechanisms. Reactors operating at high space velocity are found to be most susceptible to early failure and poisoning by product is more dangerous than by reactant. The magnitude of the jump across steady states depends solely on the Langmuir-Hinshelwood kinetic parameters and a detailed analysis of reactor behavior during the jump itself is given.

Multicomponent reversible reactions inside a porous catalyst pellet

This work deals with a solution method to handle multicomponents reversible reactions occurring inside a porous catalyst pellet. The complexity of this problem arises from the fact that the effective diffusivities and Biot number, which characterizes the external mass transfer, are different for each chemical species. In mathematical terms, this means that each chemical species has its own subspace and, therefore, when the technique of finite integral transform is applied to solve this multicomponent problem, each chemical species is associated with its own integral transform kernel. The analytical solutions obtained for this problem are compact and simple for any further manipulation. Application of this result to the catalytic reforming of C7 hydrocarbon system is shown in this paper.

The transient response of a CSTR containing porous catalyst pellets. Asymptotic solutions

Transient response of a CSTR containing porous catalyst pellets is analyzed theoretically using a matched asymptotic expansion technique. This singular perturbation technique leads directly to the conditions under which the minima of reservoir concentration occur. The existence of the minima may be used to estimate some inherent parameters of the catalyst pellet.

Hysteresis and phase transitions in a single partially internally wetted catalyst pellet: Thermogravimetric studies

The hydrogenation of cyclohexene over palladium supported in a microporous gamma-alumina pellet is studied thermogravimetrically with a view to measuring the extent of partial internal wetting associated with the different steady state branches. As many as three steady state branches having significantly different degrees of internal wetting and reaction rates, with transitions between them, are confirmed from observations of catalyst weight change. It is seen that with reduction in catalyst activity the middle branch, obtained by condensation from a vapor filled pellet, is much more prominent without showing an evaporative transition for the range of hydrogen partial pressures used here. The catalyst activity is therefore an important parameter affecting the structure of the steady state branches. Hysteresis effects are found to occur, and the thermogravimetric results also confirm the importance of history in determining the catalyst state. The measured degree of wetting is in accordance with that estimated from a mathematical model incorporating capillary condensation effects in addition to reaction-diffusion phenomena. The same model also satisfactorily interprets the reaction rate variations and transitions seen in the present work.

Effects of acidic treatments on the pore and surface properties of Ni catalyst supported on activated carbon

Activated carbon as catalyst support was treated with HCl, HNO3, and HF and the effects of acid treatments on the properties of the activated carbon support were studied by N-2 adsorption, mass titration, temperature-programmed desorption (TPD), and X-ray photoelectron spectrometry (XPS). Ni catalysts supported on untreated and treated activated carbons were prepared, characterized and tested for the reforming reaction of methane with carbon dioxide. It is found that acid treatment significantly changed the surface chemical properties and pore structure of the activated carbon. The surface area and pore volume of the carbon supports are generally enhanced upon acid treatment due to the removal of impurities present in the carbon. The adsorption capacity of Ni2+ on the carbon supports is also increased, and the increase can be closely correlated with the surface acidity. The impregnation of nickel salts decreases the surface area and pore volume of carbon supports both in micropores and mesopores. Acid treatment results in a more homogeneous distribution of the nickel salt in carbon. When the impregnated carbons are heated in inert atmosphere, there exists a redox reaction between nickel oxide and the carbon. Catalytic activity tests for methane reforming with carbon dioxide show that the activity of nickel catalysts based on the acid-treated carbon supports is closely related with the surface characteristics of catalysts. (C) 1998 Elsevier Science Ltd. All rights reserved.

Prefrontal cortex involvement in selective letter generation: A functional magnetic resonance imaging study

Cerebral responses to alternating periods of a control task and a selective letter generation paradigm were investigated with functional Magnetic Resonance Imaging (fMRI). Subjects selectively generated letters from four designated sets of six letters from the English language alphabet, with the instruction that they were not to produce letters in alphabetical order either forward or backward, repeat or alternate letters. Performance during this condition was compared with that of a control condition in which subjects recited the same letters in alphabetical order. Analyses revealed significant and extensive foci of activation in a number of cerebral regions including mid-dorsolateral frontal cortex, inferior frontal gyrus, precuneus, supramarginal gyrus, and cerebellum during the selective letter generation condition. These findings are discussed with respect to recent positron emission tomography (PET) and fMRI studies of verbal working memory and encoding/retrieval in episodic memory.

A compact superconducting magnet for magnetic resonance microscopy

Magnetic resonance microscopy (MRM) depends on the use of high field, superconducting magnet systems for its operation. The magnets that are conventionally used are those that were initially designed for chemical structural analysis work. A novel, compact magnet designed specifically for MRM is presented here, and while preserving high field, high homogeneity conditions, has a length less than one-third that of conventional systems. This enables much better access to samples, an important consideration in many MRM experiments. As the homogeneity of a magnet is strongly dependent on its length, novel geometries and optimization techniques are required to meet the requirements of MRM in a compact system. An important outcome of the stochastic optimization performed in this work, is that the use used of a thin superconducting solenoid surrounded by counterwound disk windings provides a mechanism for drastic length reductions over conventional magnet designs. (C) 1998 American Institute of Physics.

Iron(III) and iron(II) complexes of 1-thia-4,7-diazacyclononane ([9]aneN(2)S) and 1,4-dithia-7-azacyclononane ([9]aneNS(2)). X-Ray structural analyses, magnetic susceptibility, Mossbauer, EPR and electronic spectroscopy

The complexes [Fe([9]aneN(2)S)(2)][ClO4](2), [Fe([9]aneN(2)S)(2)][ClO4](3) and [Fe([9]aneNS(2))(2)][ClO4](2) ([9]aneN(2)S = 1-thia-4. 7-diazacyclononane and [9]aneNS(2) = 1,4-dithia-7-azacyclononane) have been prepared and the latter two characterised by X-ray crystallography. The Mossbauer spectra (isomer shift/mm s(-1), quadrupole splitting/mm s(-1), 4.2 K) for [Fe([9]aneN(2)S)(2)][ClO4](2) (0.52, 0.57), [Fe([9]aneN(2)S)(2)][ClO4](3) (0.25, 2.72) and [Fe([9]aneNS(2))(2)][ClO4](2) (0.43, 0.28) are typical for iron(II) and iron(III) complexes. Variable-temperature susceptibility measurements for [Fe([9]aneN(2)S)(2)][ClO4](2) (2-300 K) revealed temperature-dependent behaviour in both the solid state [2.95 mu(B) (300 K)-0.5 mu(B) (4.2 K)] and solution (Delta H degrees 20-22 kJ mol(-1), Delta S degrees 53-60 J mol(-1) K-1). For [Fe([9]aneN(2)S)(2)][ClO4](3) in the solid state [2.3 mu(B) (300 K)-1.9 mu(B) (4.2 K)] the magnetic data were fit to a simple model (H = -lambda L . S + mu L-z) to give the spin-orbit coupling constant (lambda) of -260 +/- 10 cm(-1). The solid-state X-band EPR spectrum of [Fe([9]aneN(2)S)(2)][ClO4](3) revealed axial symmetry (g(perpendicular to) = 2.607, g(parallel to) = 1.599). Resolution of g(perpendicular to) into two components at Q-band frequencies indicated a rhombic distortion. The low-temperature single-crystal absorption spectra of [Fe([9]aneN(2)S)(2)][ClO4](2) and [Fe([9]aneNS(2))(2)][ClO4](2) exhibited additional bands which resembled pseudotetragonal low-symmetry splitting of the parent octahedral (1)A(1g) --> T-1(2g) and (1)A(1g) ---> T-1(1g) transitions. However, the magnitude of these splittings was too large, requiring 10Dq for the thioether donors to be significantly larger than for the amine donors. Instead, these bands were tentatively assigned to weak, low-energy S --> Fe-II charge-transfer transitions. Above 200 K, thermal occupation of the high-spin T-5(2g) ground state resulted in observation of the T-5(2g) --> E-5(g) transition in the crystal spectrum of [Fe([9]aneN(2)S)(2)][ClO4](2). From a temperature-dependence study, the separation of the low-spin (1)A(1g) and high-spin T-5(2g) ground states was approximately 1700 cm(-1). The spectrum of the iron(III) complex [Fe([9]aneN(2)S)(2)][ClO4](3) is consistent with a low-spin d(5) configuration.

Selectively excited luminescence and magnetic circular dichroism of Cr4+-doped YAG and YGG

Site selective luminescence and magnetic circular dichroism experiments on Cr4+-doped yttrium aluminum garnet and yttrium gallium garnet have been made at low temperature. The spectral assignments for these near-IR lasing materials have been made using experimental data and ligand field calculations guided by the known geometry of the lattices. [S0163-1829(99)07003-4].

Predicting composition of leg sections with anthropometry and bioelectrical impedance analysis using magnetic resonance imaging as reference

Magnetic resonance imaging (MRI) was used to evaluate and compare with anthropometry a fundamental bioelectrical impedance analysis (BIA) method for predicting muscle and adipose tissue composition in the lower limb. Healthy volunteers (eight men and eight women), aged 41 to 62 years, with mean (S.D.) body mass indices of 28.6 (5.4) kg/m(2) and 25.1 (5.4) kg/m(2) respectively, were subjected to MRI leg scans, from which 20-cm sections of thigh and IO-cm sections of lower leg (calf) were analysed for muscle and adipose tissue content, using specifically developed software. Muscle and adipose tissue were also predicted from anthropometric measurements of circumferences and skinfold thicknesses, and by use of fundamental BIA equations involving section impedance at 50 kHz and tissue-specific resistivities. Anthropometric assessments of circumferences, cross-sectional areas and volumes for total constituent tissues matched closely MRI estimates. Muscle volume was substantially overestimated (bias: thigh, -40%; calf, -18%) and adipose tissue underestimated (bias: thigh, 43%; calf, 8%) by anthropometry, in contrast to generally better predictions by the fundamental BIA approach for muscle (bias:thigh, -12%; calf, 5%) and adipose tissue (bias:thigh, 17%; calf, -28%). However, both methods demonstrated considerable individual variability (95% limits of agreement 20-77%). In general, there was similar reproducibility for anthropometric and fundamental BIA methods in the thigh (inter-observer residual coefficient of variation for muscle 3.5% versus 3.8%), but the latter was better in the calf (inter-observer residual coefficient of variation for muscle 8.2% versus 4.5%). This study suggests that the fundamental BIA method has advantages over anthropometry for measuring lower limb tissue composition in healthy individuals.

Solution structure of alpha-conotoxin ImI by H-1 nuclear magnetic resonance

alpha-Conotoxin ImI derives from the venom of Conus imperialis and is the first and only small-peptide ligand that selectively binds to the neuronal alpha(7) homopentameric subtype of the nicotinic acetylcholine receptor (nAChR). This receptor subtype is a possible drug target for several neurological disorders. The cysteines are connected in the pairs Cys2-Cys8 and Cys3-Cys12, To date it is the only alpha-conotoxin with a 4/3 residue spacing between the cysteines, The structure of ImI has been determined by H-1 NMR spectroscopy in aqueous solution, The NMR structure is of high quality, with a backbone pairwise rmsd of 0.34 Angstrom for a family of 19 structures, and comprises primarily a series of nested beta turns. Addition of organic solvent does not perturb the solution structure. The first eight residues of ImI are identical to the larger, but related, conotoxin EpI and adopt a similar structure, despite a truncated second loop. Residues important for binding of ImI to the alpha 7 nAChR are all clustered on one face of the molecule. Once further binding data for EPI and ImI are available, the ImI structure will allow for design of novel alpha(7) nAChR-specific agonists and antagonists with a wide range of potential pharmaceutical applications.

Designs for an asymmetric gradient set and a compact superconducting magnet for neural magnetic resonance imaging

Imaging of the head and neck is the most commonly performed clinical magnetic resonance imaging (MRI) examination [R. G. Evans and J. R. G. Evans, AJR 157, 603 (1991)]. This is usually undertaken in a generalist MRI instrument containing superconducting magnet system capable of imaging all organs. These generalist instruments are large, typically having a bore of 0.9-1.0 m and a length of 1.7-2.5 m and therefore are expensive to site, somewhat claustrophobic to the patient, and offer little access by attending physicians. In this article, we present the design of a compact, superconducting MRI magnet for head and neck imaging that is less than 0.8 m in length and discuss in detail the design of an asymmetric gradient coil set, tailored to the magnet profile. In particular, the introduction of a radio-frequency FM modulation scheme in concert with a gradient sequence allows the epoch of the linear region of the gradient set to be much closer to the end of the gradient structure than was previously possible. Images from a prototype gradient set demonstrate the effectiveness of the designs. (C) 1999 American Institute of Physics. [S0034-6748(99)04910-2].

Catalytic conversion to N2O to N2 over potassium catalyst supported on activated carbon

Catalytic conversion of N2O to N-2 With potassium catalysts supported on activated carbon (K/AC) was investigated. Potassium proves to be much more active and stable than either copper or cobalt because potassium possesses strong abilities both for N2O chemisorption and oxygen transfer. Potassium redispersion is found to play a critical role in influencing the catalyst stability. A detailed study of the reaction mechanism was conducted based upon three different catalyst loadings. It was found that during temperature-programmed reaction (TPR), the negative oxygen balance at low temperatures (< 50 degrees C) is due to the oxidation of the external surface of potassium oxide particles, while the bulk oxidation accounts for the oxygen accumulation at higher temperatures (below ca. 270 degrees C). N2O is beneficial for the removal of carbon-oxygen complexes because of the formation of CO2 instead of CO and because of its role in making the chemisorption of produced CO2 on potassium oxide particles less stable. A conceptual three-zone model was proposed to clarify the reaction mechanism over K/AC catalysts. CO2 chemisorption at 250 degrees C proves to be an effective measurement of potassium dispersion. (C) 1999 Academic Press.

Periodic orbit resonances in layered metals in tilted magnetic fields

The frequency dependence of the interlayer conductivity of a layered Fermi liquid in a magnetic field that is tilted away from the normal to the layers is considered. For both quasi-one- and quasi-two-dimensional systems resonances occur when the frequency is a harmonic of the frequency at which the magnetic field causes the electrons to oscillate on the Fermi surface within the layers. The intensity of the different harmonic resonances varies significantly with the direction of the field. The resonances occur for both coherent and weakly incoherent interlayer transport and so their observation does not imply the existence of a three-dimensional Fermi surface. [S0163-1829(99)51240-X].

Synthesis of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2), a hydroxo-bridged copper(II) complex of N,N '-dimethyl-1-thia-4,7-diazacyclononane (Me-2[9]aneN(2)S). X-ray structural analysis, magnetic susceptibility, EPR and visible spectroscopy

The bis(mu-hydroxo) complex [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)](PF6)(2) (Me-2[9]aneN(2)S = N,N'-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me-2[9]aneN(2)S)(MeCN)] (PF6) with dioxygen at -78 degrees C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Angstrom, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu ... Cu 2.866(1) Angstrom. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46+/-5 cm(-1), g = 2.01+/-0.01 and theta = -0.58+/-0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g(parallel to) 2.300, g(perpendicular to) 2.063; A(parallel to) 156.2 x 10(-4) cm(-1), A(perpendicular to) 9.0 x 10(-4) cm(-1)) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a sigma(S)-->Cu-II LMCT transition at c. 34000 cm(-1). The single-crystal spectrum of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2) (273 K) reveals d-->d transitions at 14500 and 18300 cm(-1) and a weak pi(S)-->Cu-II charge-transfer band at approximately 25000 cm(-1).