Partial oxidation of methane to synthesis gas

Partial oxidation of methane to synthesis gas has been carried out over a number of transition metal catalysts under a range of conditions. It is found that the metals Ni, Ru, Rh, Pd, Ir and Pt, either supported on alumina or present in mixed metal oxide precursors, will bring the system to equilibrium. The yield of CO and H2 improves with increasing temperature in the range 650–1050 K, and decreases with increasing pressure between 1 and 20 atm. An excellent yield (92%) is obtained with a 421 N₂CH₄O₂ ratio at 1050 K and atmospheric pressure, with a space velocity of 4×10⁴ hour^–1.     

Electrosynthesis of 4,4′-dinitroazobenzene on PbO2 electrodes

Parameters which affect the electrosynthesis of 4,4-dinitroazobenzene from p-nitroaniline on platinum and PbO₂ electrodes were investigated and optimum conditions were determined. Maximum conversion efficiency for electrosynthesis was 95% with a pure -PbO₂ electrode. It was found that the electrocatalytic activity of a PbO₂ electrode depends upon its / ratio and its degree of crystallinity. The effects of the added base and water on the conversion efficiency were also elucidated.     

Suppression of the α → β-nickel hydroxide transformation in concentrated alkali: Role of dissolved cations

The presence of dissolved cations such as Al and Zn in alkaline electrolyte (6 M KOH) suppresses the -nickel hydroxide transformation. The uptake of Al (10 mol%) and Zn (30 mol%) exhibited by the active material likely stabilizes the -phase. Dissolved Al is deleterious to the performance of the nickel hydroxide electrode, whereas, dissolved Zn enhances the specific discharge capacity of nickel hydroxide by approximately 25% showing that the mode of metal uptake is different in the two cases.     

Response of the European elm bark beetle,Scolytus multistriatus (Coleoptera: Scolytidae), to isomers and components of its pheromone

Laboratory bioassays (two methods) and field tests demonstrated synergistic action of the three components [(–)-4-methyl-3-heptanol (I); (–)-2,4-dimethyl-5-ethyl-6,8-dioxabicylo[3.2.1]octane (-multistriatin) (II); and (–)--cubebene (III)] of the pheromone bouquet ofScolytus multistriatus. Individually and in pairs the components were slightly attractive; I+II was clearly the most active doublet. Indirect evidence indicates that only one of the four enantiomers of I is active. Of the , , and isomers of II, only the is active. With the addition of compound I, slightly attractive extract from mated females became nearly as active as extract from virgin females.     

Crystal Orientation Dependence of Macropore Formation in n-Si With Backside-Illumination in HF-Electrolyte

The formation of macropores on anodically biased n-type silicon with backside-illumination was investigated as a function of crystal orientation and bias voltage. Specimens were cut from bulk crystals with various orientations from {100} to {111}, polished and subjected to anodic etching in HF. The resulting pores were investigated on cleaved samples by SEM. All pores were found to grow in either a 100 direction or a 113 direction, depending on the misorientation angle. This finding applies also to the branching of a single pore. The results can be understood if the valence for the dissolution reaction is approximately 2.6 in 100 and approximately 4 in the 113 direction, and if all other directions are not allowed for the growth of pores in Si.     

Additional male mediterranean fruitfly (Ceratitis capitata wied.) Attractants from Angelica seed oil (Angelica archangelica L.)

Two sesquiterpene hydrocarbons, -copaene and -ylangene, were isolated from bioactive fractions of angelica seed oil and were shown by field bioassays to be attractive to the male Mediterranean fruit fly. Their relative attractiveness, compared with the(+)-and (–)--copaene enantiomers, are: (+)--copaene>angelica -copaene>angelica -ylangene>(–)--copaene. The enantiomer ratios for the two compounds are: -copaene, 61.4% (+), 38.6% (–); -ylangene, 91.9% (+), 8.1% (–).trans--Bergamotene was also isolated from the same fractions, but in sufficient quantity for bioassay [enantiomer ratio: 95.7% (+), 4.3% (–)].     

Hydroformylation of functional alkenes with heterodonor phosphine rhodium catalysts: substrate or ligand directed regioselectivity?

The catalytic activity and selectivity of heterodonor phosphine rhodium catalysts prepared in situ were tested in the hydroformylation of functional alkenes (ethyl acrylate, methyl methacrylate, styrene, 4-vinyl-1-cyclohexene, dicyclopentadiene and cis-1,2,3,6-tetrahydrophthalic anhydride). Systematic variation of the heterodonor atom in the ortho position of the ligand showed that the heterodonor atom has a significant influence on the activities and selectivities of the reaction. However, the activity seems to depend mainly on the modifying ligand, and the regioselectivity mainly on the substrate (i.e., the structure and functionality of the alkene). Nevertheless, regioselective control is only obtained through synergy between the substrate and the catalyst. Clear regiocontrol was observed in the hydroformylation of ,-unsaturated esters and styrene with an in situ formed o-(thiomethylphenyl)diphenylphosphine rhodium catalyst.     

Catalytic Methoxycarbonylation of Aromatic Diamines with Dimethyl Carbonate to Their Dicarbamates Using Zinc Acetate

The methoxycarbonylation of 2,4-toluene diamine and 4,4-diphenylmethane diamine with dimethyl carbonate to the corresponding dicarbamates using zinc acetate was carried out at 453 K. Zn(OAc)₂, prepared by evacuating Zn(OAc)₂2H₂O at 383 K for 2 h, yields dimethyltoluene-2,4-dicarbamate in 96% yield in 2 h, while Zn(OAc)₂2H₂O yields dimethyl-4,4-methylenediphenyldicarbamate in 98% yield at 453 K in 2 h.The structure of methyl 3-amino-4-methyl phenyl carbamate, which is one of the intermediates for the reaction of 2,4-toluene diamine with dimethyl carbonate into dimethyltoluene-2,4-dicarbamate, has been determined by measuring the NOE spectrum of ¹H NMR.     

Identification and preparation of antiinsectan dienols fromDipterocarpus kerrii tree resins

Originally isolated fromDipterocarpus kerrii, the two previously uncharacterized sesquiterpenes,1 and20, were synthesized from α-gurjunene. A novel process involvingm-chloroperoxybenzoic acid oxidation ofα-gurjunene produced20 in one step. Spectroscopic studies determined that the diene moiety in20 is nonconjugated and also found the C-4 tertiary alcohol center to have theα-configuration, while the other stereocenters have configurations matching the corresponding centers inα-gurjunene. Bioassays with termites demonstrated that20 was more toxic than1, resulting in a 50% mortality in seven days when offered toNeotermes ?dalbergiae on filter papers. The chemicals appear to result from biotransformation ofα-gurjunene. In view of its similarity to the known sesquiterpeneγ-gurjunene, we suggest that20 be referred to asγ-gurjunenol.     

Role of La2O3 in Pd-Supported Catalysts for Methanol Decomposition

Systems of Pd supported on various La₂O₃-modified -Al₂O₃ and CeO₂–Al₂O₃ catalysts were tested for catalytic methanol decomposition and characterized by means of XRD, BET, TPR, H₂-chemisorption and CO–FTIR. The addition of lanthanum significantly improved the selectivity of CO and H₂ for all the catalysts but showed a different influence on the catalytic activity in two systems. Methanol conversion decreased on La₂O₃-modified Pd/-Al₂O₃ catalysts, in line with the reduction of Pd dispersion, while the addition of La₂O₃ improved the dispersion of Pd and reinforced Pd–CeO₂ interaction for La₂O₃-modified Pd/CeO₂–Al₂O₃ catalysts, which resulted in a high production rate of CO and H₂. Thus, a synergistic effect between CeO₂ and La₂O₃ was observed on -Al₂O₃-supported Pd catalyst for methanol decomposition.     

Transport of phosphorus forms and of nitrate through a clay soil under grass and cereal production

Many nutrients are lost from soil to water viatile drains. However, there are very few reliable studies of such phosphorus(P)losses under Swedish agriculture practices, especially in connection tofertiliser and slurry applications and related to nutrient balances. Tile drainlosses were measured from nine experimental plots in south-west Sweden; fourplots were measured for 7 years and five plots for 2–3 years. Cereals,mainly spring barley (Hordeum vulgare, L.) and oats(Avena sativa, L.), were grown in six plots, while oneplotwas cultivated with grass, timothy (Phleum pratense L.)andmeadow fescue (Festuca pratensis, L.), one with lucerne(Medicago sativa, L.) and meadow fescue (F.pratensis, L.), and the last one was a set-aside withgrass (Lolium perenne, L. and Trifoliumrepens, L.) that was neither fertilised nor used for crop removal.Attention was paid to the forms in which P was transported to water since thishas important ecological implications. Average losses of particulate P (PP)fromthe set-aside land was significantly lower than from the cerealproduction, but the average losses of soluble reactive P (SRP) and dissolvednonreactive P (DUP) were the same. Average loss of PP from the grass ley during 3years (0.09 kg per ha^–1 y^–1) wassignificantly less than the losses from cereal production. Total P loss of 0.3kg per ha^–1 y^–1 was equal to the averagelossfrom the Swedish monitoring network of observation fields. Compared to theaverage nitrate-nitrogen (NO₃-N) leaching, which was 7 kg perha^–1 y^–1 from cereals, the NO₃-Nleaching was very low from the plots with lucerne-grass and set-aside.After applying and directly ploughing in 80 kg ha^–1 ofsuperphosphate for cereal production in November 1998, 0.6–1.8 kgSRP ha^–1 y^–1 was lost through the drain tiles.Surface application of cattle slurry in spring 1999 to the grass ley alsoresulted in a very pronounced increased base level of SRP. This paper documentsthe importance of applying slurry during dry conditions and of placingfertiliser into the soil according to crop requirements in the time perspectiveof one year.     

Polyimides based on “multiring” flexible diamines

The five benzene rings-containing (hereafter for convenience, referred to as five-ringrd) diamines ad-bis[4-(4-aminophenoxy)phenyl]-1,4 (or 1,3)-diisopropylbenzene (p- or m-3) were prepared by a nucleophilic substitution of ,-bis(4-hydroxyphenyl)-1, 4 (or 1,3)-diisopropylbenzene (p- or m-1) with p-chloronitrobenzene in the presence of K₂CO₃ and then hydro-reduced. The polyimides were synthesized from diamine 3 and various aromatic dianhydrides via the two-stage procedure that include ring-opening polyaddition in DMAc to give poly(amic acid)s, followed by thermal conversion to polyimides. The poly(amic acid)s had inherent viscosities of 0.63–1.54 dL/g depending on the dianhydrides used. Almost all the poly(amic acid)s could be solution-cast and thermally converted into transparent, flexible, and tough polyimide films. These polyimides have glass transition temperatures in the range of 186–290°C and almost no weight loss up to 500°C in air or nitrogen atmosphere. The polyimide obtained from pyromellitic dianhydride and diamine m-3 showed two endothermic peaks of 270 and 300°C on the diagram of differential scanning calorimetry (DSC), and the other polyimides showed no endotherms on their DSC traces.     

Effect of the naturally occurring salt ‘Kanwa’ as a fertilizer on the productivity ofStylosanthes in the subhumid zone of Nigeria

Soil nutrient deficiencies pose a serious limitation to higher crop and forage yields in the Nigerian subhumid zone. Some of the deficiencies may be alleviated by using as a fertilizer a salt mined locally called Kanwa which is traditionally used as a cattle lick. Yields ofStylosanthes hamata cv Verano andS. guianensis cv Cook seed and dry matter increased with Kanwa application at different locations. The effect of Kanwa was enhanced when phosphorus was adequately supplied. Improvements to soil physical properties were proportional to the yield of the legume. The implications of good quality fodder and improved soil conditions in Agro-pastoral Systems in the Nigerian SHZ are discussed.     

High‐activity catalyst of SO 4 2− /ZrO2 supported on γ‐Al2O3 for n‐butane isomerization

A series of Al₂O₃supported SO ₄ ^2– /ZrO₂ superacid catalysts (named SZ/Al₂O₃) were prepared by a precipitation method and their catalytic behavior for nbutane isomerization at low temperature in the absence of H₂ and at high temperature in the presence of H₂ was studied in this paper. The catalytic activities of some of these catalysts were enhanced significantly at both low and high temperatures. At 250°C after 6 h on stream, the steady activity of the most active sample, 60%SZ/Al₂O₃, is about two times higher than that of conventional SZ. The texture properties of catalysts were studied by the methods of XRD and the adsorption of N₂. Experimental evidence of IR of adsorbed pyridine indicates that the significant activity enhancements of SZ/Al₂O₃ catalysts are caused by the increasing of the amount of strong acid sites.     

Residual effects of growing mungbean and uridbean on the yield and nitrogen uptake of a succeeding wheat crop

A two year field experiment was carried out at the Indian Agricutural Research Institute, New Delhi - 110012, India to assess the effect of mungbean (Vigna radiata L.) and uridbean (Vigna mungo L.) residues on the yield and N uptake of a succeeding wheat crop as compared to sorghum fodder. Sorghum produced 3.5–7.5 times more dry matter and removed 2–3 times more nitrogen than mungbean or uridbean during same duration (80 ± 10 days) of their growth. Without N application the grain yield of wheat following mungbean and uridbean (without residue incorporation) was 0.45 and 0.48 t ha^–1 more than the yield of wheat following sorghum fodder. These yields were equivalent to that predicted when 36 and 38 kg urea-N ha^–1, respectively, was directly applied to wheat. The residual effects of these grain legumes were higher when succeeding wheat was fertilized with 60 kg urea-N ha^–1; at this level mungbean and uridbean spared 52 and 43 kg urea-N ha^–1, respectively, in succeeding wheat. The residual effect of mungbean and uridbean further increased when their residue was incorporated in soil; with this practice they spared 94 and 115 kg urea-N ha^–1, respectively, without N application to wheat and 74 and 82 kg urea-N ha^–1, respectively, with an application of 60 kg urea-N ha^–1 to wheat.Mungbean and uridbean, without residue incorporation, increased aboveground plant-N uptake of succeeding wheat by 11.5–34.9 and 10.8–34.0 kg N ha^–1, respectively; whereas with residue incorporation, they increased aboveground plant-N content of succeeding wheat by 26.1–45.8 and 32.7–47.7 kg N ha^–1, respectively.The results of the present study indicate that there is both an indirect sparing effect and a direct residual effect of mungbean and uridbean on the nitrogen needs of succeeding wheat, more so when their residues are incorporated in soil.     

Phase transitions and dimensional and morphological changes in an “Aluminum Hydroxide-Alumina” system under a shock-wave action

A method is proposed to study the sequence of phase transitions in powdered materials under a shock-wave action. It is shown that the aluminum hydroxide-alumina system has the following sequence of phase transformations under a shock-wave action: bayerite boehmite -Al₂O₃ -Al₂O₃. It is found that there are no transitional high-temperature modifications of alumina. A method is developed for obtaining a submicron alumina powder, which allows obtaining materials with a controlled phase composition, including a thermodynamically stable -modification of Al₂O₃. The specific features of the morphological structure and the phase and structural characteristics of powders after a shock-wave action are considered.Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 1, pp. 110–119, January–February, 2005.     

Catalytic properties of new Cu based catalysts containing Zr and/or V for methanol synthesis from a carbon dioxide and hydrogen mixture

Pure unsupported copper is a poor catalyst for CH₃OH synthesis from CO₂+H₂ when it is compared to Cu coprecipitated with Zr or Zr+V in which case its selectivity and yield in methanol are strongly enhanced. The two Zr and V components added to pure Cu are shown to be textural promoters towards zerovalent Cu which participate to the building of the active sites. Methanol formation on these catalysts is a structure insensitive reaction with respect to the metallic Cu dosed by N₂O surface decomposition.     

Enantioselective hydrogenation of α-ketoesters over Pt/alumina modified with cinchonidine: theoretical investigation of the substrate-modifier interaction

Enantio-differentiation in the asymmetric hydrogenation of -ketoesters to -hydroxyesters over platinum catalysts modified with cinchona-alkaloid modifiers occurs through interaction of the ketoester with the cinchona modifier. The structure of the probable transition complex has been calculated for the system methyl pyruvate (substrate) cinchonidine (modifier) using molecular mechanics and quantum chemistry techniques at both ab initio and semiempirical levels. The calculations suggest that protonated cinchonidine is energetically more likely to interact with the substrate and that the crucial interaction occurs via hydrogen bonding of the quinuclidine nitrogen and the oxygen of the -carbonyl moiety of methyl pyruvate. In this complex the methyl pyruvate is transformed into a half-hydrogenated species which is adsorbed on the platinum surface and on hydrogenation yields the product methyll actate. Theoretical studies indicate that adsorption of the complex leading to (R) -methyl lactate is energetically more favourable than that of the corresponding complex which yields (S) -methyl lactate, which may be the key for the enantio-differentiation.     

Synthesis and properties of aromatic polyesters and brominated polyesters derived from α,α′-bis(4-hydroxyphenyl)-1,4(or 1,3)-diisopropylbenzene

The interfacial polycondensation technique was used for the preparation of polyarylates and brominated polyarylates. Polyarylates and brominated polyarylates were prepared by mixing a solution of diacid chloride such as terephthaloyl chloride, isophthaloyl chloride, or their mixture in dichloromethane with an aqueous alkaline solution of ,-bis(4-hydroxyphenyl)-1,4(or 1,3)-diisopropylbenzene or ,-bis(4-hydroxy-3,5-dibromophenyl)-1,4(or 1,3)-diisopropylbenzene using triethylbenzylammonium chloride as the phase transfer agent. Moderate to high molecular weight polyarylates with _inh up to 1.27 dL/g were obtained, and most of them could be cast into tough and flexible films depending on the polymer composition. In general, polymers containing more 1,3-isomer or isophthaloyl chloride moieties gave transparent and flexible films and had lower glass transition temperatures and higher solubility. Although these polymers have two isopropylidene linkages in their repeating units, they still exhibit moderately high thermal stability and show no obvious weight loss before 400 °C. The introduction of bromine on the polymer backbone caused a decrease of inherent viscosity, crystallinity, and thermal stability of the polyarylates, while causing an increase in glass transition temperature and a great enhancement of fire retardancy.