Chemistry of hydrogen sulphide under coal liquefaction conditions: 1. Modelling hydrogen transfer catalysis

The work reported here represents initial attempts to develop a complete kinetic and mechanistic understanding of the reaction chemistry of H₂S under coal liquefaction conditions, using both model systems and coal. Hydrogen sulphide was found to promote/catalyse the transfer of hydrogen from tetralin to 2-hydroxyquinoline (2-HOQ). The presence of H₂S can increase the rate of hydrogen transfer from tetralin to 2-HOQ by a factor of 10 compared with the same reaction run in the absence of H₂S. The energy of activation for hydrogen transfer was found to decrease by ≈5 kcal mol⁻¹ in the presence of H₂S. The presence of H₂S was also found to promote loss of oxygen from 2-HOQ to form small amounts of quinoline. No evidence of CC or CN bond cleavage in 2-HOQ was noted under any of the reaction conditions studied. These results suggest that the presence of H₂S reduces the temperatures necessary to promote effective hydrogen transfer from tetralin by 50–75 °C. Moreover, they imply that similar effects occur in H₂S-promoted coal liquefaction.     

Effect of process distillation on mutagenicity and cell-transformation activity of solvent-refined,coal-derived liquids

Blended SRC-II process streams, representing a full boiling range distillate material, were fractionally distilled into non-overlapping 50 °F cuts with boiling points between 300 and 850 °F. Another set of 18 distillate cuts were obtained with boiling points ranging between 138 and 1055 °F. Distillate cuts were assayed for mutagenic activity using the histidine reversion assay with Salmonella typhimurium strains TA98, TA100, TA1535 and TA1537, as well as for mammalian-cell transformation activity in the Syrian hamster embryo test, and DNA damage in the prophage induction assay. Samples were also separated into chemical class fractions by alumina column chromatography and analysed by high resolution gas chromatography so that the chemical composition of the cuts could be related to their relative activity in the different assays. In the mammalian cell transformation and microbial mutagenicity assays, significant activity was found almost exclusively in distillate cuts with components boiling > 700 °F, with the highest activity in the transformation assay observed for cuts > 800 °F. All of the distillate cuts showed increased levels of DNA damage as expressed by lambda prophage induction in Escherichia coli 8177. However, the greatest activity was associated with distillate cuts with boiling points in the 800 °F + range. Chemical analysis of the 50 °F distillate cuts showed a variety of polycyclic aromatic hydrocarbons (PAH) and amino-PAH compounds to be present in the distillate cuts boiling > 700 °F and essentially absent from cuts boiling < 700 °F. The sample set of non-overlapping (50 °F) cuts were reblended according to the proportions of each cut found in the original blend material. These reblended composites were then assayed to compare their activity with that predicted from the activities of the component distillate cuts. The reblending experiments indicated the microbial mutagenicity response was essentially additive. Mammalian cell transformation activities were non-additive, indicating a compositional effect on the expression of transforming agents in the complex mixture.     

Chemistry of hydrogen sulphide under coal liquefaction conditions: 2. Synergistic effects of H2S and the mixed solvent system tetralin and tetrahydroquinoline on liquefaction of a moderately reactive coal

A preliminary study was undertaken to evaluate the effects of mixed solvents and added H₂S on the overall conversions of a moderately reactive coal (Wyodak-2) as defined by tetrahydrofuran solubility. Conversion efficiencies were measured as a function of time and of H₂S concentration in the H₂S-tetrahydroquinoline (THQ) solvent system. The specific solvent systems studied included tetralin and mixtures of tetralin and THQ, with and without H₂S. In all cases, coal conversion was enhanced by the presence of H₂S, THQ or both, relative to the use of tetralin alone. Conversion as a function of THQ concentration was also determined. The relative abilities of the various combinations to effect conversion were found to be as follows: tetralin < 5 wt% THQ-tetralin < 3 wt% H₂S-tetralin < 10 wt% THQ-tetralin = 20 wt% THQ-tetralin < 3 wt% H₂S-20 wt% THQ-tetralin. From these results, it is concluded that both H₂S and THQ operate synergistically to provide enhanced yields of high-quality coal liquids. The relations between conversion, H₂S concentration and nitrogen incorporation are discussed.     

Coal liquefaction using a hydrogenated creosote oil solvent: H-atom transfer from hydrogen donor components in the solvent

The presence of hydroaromatic, hydrogen donor components in a coal-derived solvent is one of the more important factors in the successful operation of a non-catalytic coal liquefaction process. Various hydrogen donor species present in a hydrogenated creosote oil have been identified. Their rate of disappearance under conditions that are consistent with a short residence time coal liquefaction process has been used to rank the reactivities of the various hydrogen donors. 1,2,3,10b-Tetrahydrofluoranthene was found to be an exceptional donor while 4,5-dihydropyrene, the hexahydropyrenes and 9,10-dihydrophenanthrene were found to be quite active. Sym.-octahydrophenanthrene and 2a,3,4,5-tetrahydroacenaphthene exhibited moderate activity. Tetralin and the four methyltetralin isomers were found to be unreactive under the coal liquefaction conditions employed.     

An X-ray study of particulate solids flow in a cylindrical bunker

The noise generated by a ball mill during a batch grinding operation is investigated and the results show that, for a given ore, the noise levels may vary with time of grind, ore charge weight and mill speed. The role of the ore in absorbing noise energy is suggested as a possible control variable for the grinding process and as an indicator of product size distribution. The relationship between ore types and mill noise is also examined and, under conditions of wet grinding, it is demonstrated that mill noise analysis can indicate ore type and may have a possible use as a grindability-type parameter.     

Effect of humidity and temperature on the adhesive strength of pressure sensitive adhesives

This paper reports the effect of humidity and temperature on the adhesive strength of a pressure sensitive adhesive (Flexbond 150) used to bond Mylar films. It has been found that, ill general, the adhesive strength decreases significantly with an increase in temperature. The effect of humidity on the bonding strength, however, was found to be process dependent. The sample preparation conditions, e.g., press weight for the bonding and the press time, are important in determining the humidity effect. The water sorption isotherm A 24°C for the adhesive was also determined. The amount of water sorbed by the adhesive at 95 percent relative pressure was found to be less than one weight percent.     

Metal—Metal Triple Bonds Possessing the Electron-Rich σ2π4δ2δ*2 Electronic Configuration

The structural and reaction chemistry of dimetal complexes containing metal—metal triple bonds of the electron-rich type (σ²π⁴δ²δ^*2 configuration) is reviewed. Metal cores possessing this unit are Mo²⁺₂, Re⁴⁺₂, Ru⁶⁺₂, and Os⁶⁺₂, of which only Re⁴⁺₂ has yet been subject to a detailed study. Emphasis is placed upon the more recent developments in this field.     

Ionization of Acetylacetone in Me2SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

Rate constants for the reversible deprotonation of acetylacetone were measured in carboxylate and amine buffers in water and in 50%, 90% and 95% Me₂SO at 20°C. The Brønsted plot for the carboxylate ions is curved in the Me₂SO—water mixtures, but straight in water. The curvature is in the direction predicted by the Reactivity—Selectivity Principle (RSP). However, the Brønsted plot for the reaction with primary amines is straight in all solvents. This suggests that the curvature observerd with the carboxylate ions is caused by loss of solvation of the base; this loss of solvation is ahead of bond formation in the transition state rather than being a manifestation of the RSP. (Note that all Brønsted plots are based on pK_a values measured in the respective solvents.) The intrinsic rate constant (k₀) for proton transfer increases with the addition of Me₂SO, and more so with the carboxylate buffers than with the amines. This increase in k₀ is attributed to delayed solvation of the developing enolate ion in the transition state; with the carboxylate buffers, an additional factor is the early loss of solvation of the base. The various solvation effects observed in this study can all be understood in the context of the Principle of Imperfect Synchronization (PIS).     

Effect of sieved fractionation on the physical,flow and hydration properties of Boscia senegalensis Lam., Dichostachys glomerata Forssk. and Hibiscus sabdariffa L. powders

Food Science and Biotechnology - This study aimed at evaluating the effect of successive grinding and sieving processes on the physicochemical properties of powders obtained from Boscia...