An NMR study of acid sites on chlorided alumina catalysts using trimethylphosphine as a probe

The MAS-NMR spectra of adsorbed trimethylphosphine (TMP) were used to determine the concentration of Brønsted and Lewis acid sites on pure and chlorinated-Al₂O₃ samples. Chlorination with CHCl₃,CCl₄ or AlCl₃ promoted the formation of Brønsted acid centers, which are characterized by the protonated adduct of TMP. This adduct has a³¹P chemical shift of ca. –3.8 ppm and a J_P–H scalar coupling of 517 Hz. Additional resonances in the –44 to –54 ppm range are attributed to Lewis acid-base pairs. In some cases a partially resolved J_P–Al coupling is observed, which confirms the assignment. Upon thermal treatment of a chlorinated sample at temperatures > 200°C, the concentration of Brønsted acid centers decreased; the concentration of one type of Lewis acid increased and another remained almost constant. In a parallel set of experiments the initial conversion ofn-hexane at 150°C and the yields of cracking and isomerization products were determined. Comparable functional relationships were observed between the loss of Brønsted acid sites and the decrease in yields of both cracking and isomerization products. These results suggest that Bransted acidity is responsible for the cracking and isomerization ofn-hexane over chlorided aluminas at 150°C.     

A three-dimensional eigenfunction expansion approach for singular stress field near an adhesively-bonded scarf joint interface in a rigidly-encased plate

A three-dimensional eigenfunction expansion approach for determination of the singular stress field in the vicinity of an adhesively-bonded scarf joint interface in a plate, with its top and bottom surfaces being encased, fully or partially, between infinitely rigid blocks is presented. The plate is subjected to extension/bending (mode I) and in-plane shear/twisting (mode II) far-field loading. Both the adhesive layer and plate materials are assumed to be isotropic and elastic. The boundary conditions that are prescribed on the end-faces (free, fixed and lubricated) of the plate as well as those, prescribed at the bottom or top surface of the scarf-bonded plate on either side of the interface between the plate and adhesive layer materials (fixed-fixed, free-fixed and fixed-free), are exactly satisfied. Numerical results include the dependence of the lowest eigenvalue (or most severe stress singularity) on the wedge aperture angle of the plate material. Variation of the same with respect to the shear moduli ratio of the constituent plate and adhesive layer materials is also an important part of the present investigation. Hitherto unobserved interesting and physically meaningful conclusions in regards to the fixed edge singularity and delamination type flaw sensitivity of an adhesively bonded plate surface are also presented. Finally, hitherto unavailable results, pertaining to the through-width variations of stress intensity factors corresponding to symmetric and skew-symmetric sinusoidal loads that also satisfy the boundary conditions on the end-faces of the adhesively bonded plate, in the vicinity of the scarf joint interface, under investigation, bridge a longstanding gap in the bonded joint stress singularity/fracture mechanics literature.     

Metabolic fingerprinting of biofluids by infrared spectroscopy: modeling and optimization of flow rates for laminar fluid diffusion interface sample preconditioning

The laminar fluid diffusion interface (LFDI) is a microfluidic tool that manipulates the composition of liquid mixtures by exploiting differences among diffusion coefficients of the dissolved components. One application is the preprocessing of (bio)fluids prior to spectroscopic characterization. For example, in the case of infrared (IR) spectroscopy, the technique can improve sensitivity to low-concentration serum metabolites. The practical benefit is "metabolic fingerprinting" measurements that are more sensitive to low-concentration metabolites than are the counterpart measurements for the original serum sample. Optimal use of the LFDI technique has proven elusive, since the composition of the product of interest is very sensitive to the choice of flow rates for the liquid streams entering and emerging from the LFDI channel. To provide the basis for optimal use, this study had the objective of developing a simulation package that predicts the composition of the LFDI product, given the LFDI structural and operating parameters. To demonstrate the utility of the simulations, composition of the LFDI products predicted for two illustrative sets of trials were compared with experimental data. The flow rates thus derived provided a LFDI product that is relatively rich in serum metabolites, while largely depleted of protein, and very well suited for subsequent IR spectroscopic characterization.     

Cure and properties of unfoamed polyurethanes based on uretonimine modified methylene–diphenyl diisocyanate

The curing behaviour of a series of polyurethanes based on modified methylene–diphenyl diisocyanate (MDI) and poly(propylene oxide) polyols was studied using isothermal Fourier‐transform infrared spectroscopy (FTIR), temperature‐ramped differential scanning calorimetry (DSC) and adiabatic exotherm experiments. The effects of catalyst type and content, and of polyol molecular weight and functionality on the curing behaviour of the material were investigated. Increasing catalyst concentration or decreasing the polyol molecular weight raised the rate of reaction and shifted the DSC peak exotherm temperature to lower temperatures, but the heat of reaction was effectively constant. A marked increase in reaction rate was observed when a 1 °‐alcohol‐based polyol (from ethylene oxide end‐capping) was used in place of the standard poly(propylene oxide) end‐capped 2 °‐polyols. FTIR isocyanate conversion during polyurethane formation for a range of dibutyltin dilaurate (DBTDL) concentrations was satisfactorily fitted to second‐order kinetics. An approximately linear relationship between DBTDL catalyst concentration and reaction rate constant was found, but increasing the concentration of DBTDL was found to have no significant effect on the magnitude of the activation energy. The activation energy for polymerization was found to be independent of the molecular weight of the diol or triol systems. Dynamic mechanical thermal analysis revealed a linear increase of the glass transition temperature with decreasing triol weight fraction, and was in good agreement with a theoretical model based on copolymer and crosslinking effects. © 2000 Society of Chemical Industry     

The fractionation of milk fat from a solvent at low temperatures

Summary A procedure for fractionating milk fat from a solvent at low temperatures has been developed. This procedure consists of freezing out fractions of the fat from solvent (Skelly Solve A) at progressively lower temperatures —7°, —13°, —23°, —53°C., with the remaining filtrate taken as a final fraction. In physical appearance these fractions vary from a dry white powder to a reddish-yellow oil; in melting point from 53°C. to —10.6°C.; in iodine number from 8.29 to 58.37; and in saponification equivalent from 262.8 to 235.2. The saponification equivalents do not change in the same order as the other properties mentioned. This fat fractionation effects a simplification of milk fat and makes available less complex portions of the natural glyceride mixtures for detailed study of the composition, configuration, and other properties. Some of these studies are now being carried out and will be reported later.     

Catalytic conversion of methane to benzene over Mo/ZSM-5

Dehydroaromatization of methane to benzene occurs over a 2 wt% Mo/ZSM-5 catalyst at 700C under non-oxidizing conditions. Following an initial induction period, during which CH₄ reactant reduces the original Mo⁶⁺ ions in the zeolite to Mo₂C and deposition of coke occurs, a benzene selectivity of 70% at a CH₄ conversion of 8–10% could be sustained for more than 16 h. X-ray photoelectron spectroscopy and X-ray powder diffraction measurements indicate that the reduced Mo is highly dispersed in the channels of the zeolite. Initial activation of CH₄ reactant occurs on Mo₂C sites, leading to the formation of C₂H₄ as the primary product. The latter then undergoes subsequent oligomerization reactions on acidic sites of the zeolite to form aromatic products.