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).     

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.     

MASS TRANSFER IN GAS-SPARGED POROUS ELECTRODES

The electrochemical limiting current method was used to measure mass transfer coefficients with cocurrent upward gas-liquid flow in packed bed electrodes. Liquid-solid and overall gas-solid coefficients were determined from limiting current data in the presence of inert or reactive gas flows with the use of a plug flow model. The presence of inert gas flow increased mass transfer coefficients over those in single-phase flow by a factor of up to 1.7. As a result of boundary layer penetration by gas bubbles, sparging with reactive gas increased mass transfer rates by a factor of up to 3.5.     

MODELING LIQUID MASS TRANSFER IN HIGEE SEPARATION PROCESS

Correspondence concerning this paper should be addressed to Professor Richard S.H. Mah. Hsien-Hsin Tung is now affiliated with Department of Chemical Engineering, California Institute of Technology

Penetration theory is used to describe the liquid mass transfer in Higee separation process. Within a possible range of effective areas, it is shown that the predicted mass transfer coefficients are in reasonable agreement with the estimated mass transfer coefficients. The estimated coefficients were calculated from the experimental data and the possible effective areas. Hence it is concluded the penetration theory is generally applicable to describe liquid mass transfer in Higee separation process. The comparison also suggests that liquid mixing at the junctions of packing materials may be more complete in Higee process than in traditional process.     

Trends in industrial use of vegetable oils in coatings

Alkyd resins continue to be a major factor in coatings. Increased oil consumption in alkyd manufacture is not expected to be significant. Projections indicate a modest growth in total coatings usage at 2–3% per year. The industry is facing diverse coating performance demands that will bring unusual, more costly ingredients into use, probably at the expense of traditional oil-based alkyd resins. Offsetting this oil usage decline, perhaps, will be the continuing cost advantage of the relatively low-priced vegetable oils and the general versatility of alkyd resins. Increased use of oil-based resins is expected in emulsion (latex) paint modifiers to improve adhesion and early water resistance. The coatings industry, at least in maintenance and industrial coatings, is adopting a cost/sq ft/year economic evaluation, facotoring in the useful life of the coating.     

Detection of 4-aminocarminic acid in beverages and cake glaze from the German market: a food additive not approved in the EU

In the European Union, carminic acid and its ammonium, calcium, potassium or sodium salts and its aluminium lakes are approved as food additive E120. In beverages obtained from the German market 4-aminocarminic acid (“acid-stable carmine”) was detected by HPLC–PDA and LC–MS/MS. Isolation of the colorant from a liquid dye preparation used for the production of a beverage sample and subsequent NMR analysis confirmed the presence of 4-aminocarminic acid. Synthesis of ¹⁵N-4-aminocarminic acid clearly demonstrated that “acid-stable carmine” is not the ammonium salt of carminic acid, which is approved as food additive in the European Union. In fact, nitrogen in “acid-stable carmine” is covalently bound. The molecular structure of carminic acid is chemically modified and 4-aminocarminic acid does not comply with the specifications laid down for E120 in Commission Regulation (EU) No 231/2012. 4-Aminocarminic acid was also detected in the red-colored glaze of a raspberry cake and in the liquid dye preparation used for coloring this glaze.