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At least 55 records · Page 3

Electron-impact promoted fragmentation of alkyl-n-/1-phenylethyl/-carbamates of primary, secondary and tertiary alcohols.

The mass spectra of twenty alkyl carbamates derived from primary, secondary, and tertiary alcohols are investigated, using deuterium labeling and high-resolution mass spectrometry. Several of the primary and secondary alcohol derivatives are found to yield an ion formally equivalent to the product ion of a McLafferty rearrangement. Deuterium labeling, however, revealed a lack, in these carbamate derivatives, of the usual site specificity associated with the McLafferty rearrangement. A double hydrogen rearrangement process was observed in the mass spectra of several carbamates derived from tertiary alcohols.

Pereira, W. E.

The effects of alcohol on driver performance in a decision making situation

The results are reviewed of driving simulator and in-vehicle field test experiments of alcohol effects on driver risk taking. The objective was to investigate changes in risk taking under alcoholic intoxication and relate these changes to effects on traffic safety. The experiments involved complex 15 minute driving scenarios requiring decision making and steering and speed control throughout a series of typical driving situations. Monetary rewards and penalties were employed to simulate the real-world motivations inherent in driving. A full placebo experimental design was employed, and measures related to traffic safety, driver/vehicle performance and driver behavior were obtained. Alcohol impairment was found to increase the rate of accidents and speeding tickets. Behavioral measures showed these traffic safety effects to be due to impaired psychomotor performance and perceptual distortions. Subjective estimates of risk failed to show any change in the driver's willingness to take risks when intoxicated.

Allen, R. W.

Reduced mental capacity and behavior of a rider of a bicycle simulator under alcohol stress or under dual task load

Experiments were carried out on a bicycle simulator with alcohol administration and a binary choice task in separate sessions, intending to reduce the subject's mental capacity. Before and after such sessions a visual evoked response measurement was done. The subject's performance was analyzed with describing function techniques. The results indicate that the alcohol affects the course-following task as well as the balancing task. The binary choice task is more specifically influencing the course-following task. The dual task shows a more pronounced effect on the recovery of the evoked response. The alcohol is delaying the recovery curve of the evoked response. A tentative explanation can be given which agrees with the performance data.

Soede, M.

Three methods for in situ cross-linking of polyvinyl alcohol films for application as ion-conducting membranes in potassium hydroxide electrolyte

Three methods of in situ cross-linking polyvinyl alcohol films are presented. They are: (1) acetalization with a dialdehyde such as glutaraldehyde, (2) acetalization with aldehyde groups formed by selective oxidative cleaving of the few percent of 1,2 diol units present in polyvinyl alcohol, and (3) cross-linking by hydrogen abstraction by reaction with hydrogen atoms and hydroxyl radicals from irradiated water. For the third method, improvement in film conductivity in KOH solution at the expense of mechanical strength is obtained by the presence of polyacrylic acid in the polyvinyl alcohol films. Resistivities in 45 percent KOH are given for in situ cross-linked films prepared by each of the three methods.

Philipp, W. H.

In situ self cross-linking of polyvinyl alcohol battery separators

A battery separator was produced from a polyvinyl alcohol sheet structure which was subjected to an in situ, self crosslinking process by selective oxidation of the 1,2 diol units present in the polyvinyl alcohol sheet structure. The 1,2 diol units were cleaved to form aldehyde end groups which subsequently crosslink through acetalization of the 1,3 diol units of the polyvinyl alcohol. Selective oxidation was achieved using a solution of a suitable oxidizing agent such as periodic acid or lead tetraacetate.

Philipp, W. H.

Fumigation of Alcohol in a Light Duty Automotive Diesel Engine

A light-duty automotive Diesel engine was fumigated with methanol in amounts up to 35% and 50% of the total fuel energy respectively in order to determine the effect of alcohol fumigation on engine performance at various operating conditons. Engine fuel efficiency, emissions, smoke, and the occurrence of severe knock were the parameters used to evaluate performance. Raw exhaust particulate and its soluble organic extract were screened for biological activity using the Ames Salmonella typhimurium assay. Results are given for a test matrix made up of twelve steady-state operating conditions. For all conditions except the 1/4 rack (light load) condition, modest thermal efficiency gains were noted upon ethanol fumigation. Methanol showed the same increase at 3/4 and full rack (high load) conditions. However, engine roughness or the occurrence of severe knock limited the maximum amount of alcohol that could be fumigated. Brake specific nitrogen oxide concentrations were found to decrease for all ethanol conditions tested. Oxides of nitrogen emissions, on a volume basis, decreased for all alcohol conditions tested. Based on the limited particulate data analyzed, it appears that ethanol fumigation, like methanol fumigation, while lowering the mass of particulated emitted, does enhance the biological activity of that particulate.

Broukhiyan, E. M. H.

Screening For Alcohol-Producing Microbes

Dye reaction rapidly identifies alcohol-producing microbial colonies. Method visually detects alcohol-producing micro-organisms, and distinguishes them from other microbial colonies that do not produce alcohol. Method useful for screening mixed microbial populations in environmental samples.

Schubert, Wayne W.

Effect of alcohol addition on shock-initiated formation of soot from benzene

Soot formation in benzene-methanol and benzene-ethanol argon-diluted mixtures was studied behind reflected shock waves by monitoring the attenuation of an He-Ne laser beam. The experiments were performed at temperatures 1580-2250 K, pressures 2.0-3.0 bar, and total carbon atom concentrations (2.0-2.7) x 10 to the 17th atoms/cu cm. The results obtained indicate that the addition of alcohol suppresses the formation of soot from benzene at all temperatures, and that the reduction in soot yields is increased with the amount of alcohol added. The analysis of the results indicates that the suppression effect is probably due to the oxidation of soot and soot precursors by OH and the removal of hydrogen atoms by alcohol and water molecules.

Frenklach, Michael

Compression-ignition engine performance with undoped and doped fuel oils and alcohol mixtures

Several fuel oils, doped fuel oils, and mixtures of alcohol and fuel oil were tested in a high-speed, single-cylinder, compression-ignition engine to determine power output, fuel consumption, and ignition and combustion characteristics. Fuel oils or doped fuel oils of high octane number had shorter ignition lags, lower rates of pressure rise, and gave smoother engine operation than fuel oils or doped fuel oils of low octane number. Higher engine rotative speeds and boost pressures resulted in smoother engine operation and permitted the use of fuel oils of relatively low octane number. Although the addition of a dope to a fuel oil decreased the ignition lag and the rate of pressure rise, the ensuing rate of combustion was somewhat slower than for the undoped fuel oil so that the effectiveness of combustion was practically unchanged. Alcohol used as an auxiliary fuel, either as a mixture or by separate injection, increased the rates of pressure rise and induced roughness. In general, the power output decreased as the proportion of alcohol increased and, below maximum power, varied with the heating value of the total fuel charge.

Moore, Charles S

Effect of Water-Alcohol Injection and Maximum Economy Spark Advance on Knock-Limited Performance and Fuel Economy of a Large Air-Cooled Cylinder

An investigation was conducted to determine the effect of a coolant solution of 25 percent ethyl alcohol, 25 percent methyl alcohol, and 50 percent water by volume and maximum-economy spark advance on knock-limited performance and fuel economy of a large air-cooled cylinder. The knock-limited performance of the cylinder at engine speeds of 2100 and 2500 rpm was determined for coolant-fuel ratios of 0.0, 0.2, and 0.4. The effect of water-alcohol injection on fuel economy was determined in constant charge-air flow tests. The tests were conducted at a spark advance of 20 deg B.T.C. and maximum-economy spark advance.

Heinicke, Orville H.

Microgravity Compatible Reagentless Instrumentation for Detection of Dissolved Organic Acids and Alcohols in Potable Water

The Organic Acid and Alcohol Monitor (OAAM) program has resulted in the successful development of a computer controlled prototype analyzer capable of accurately determining aqueous organic acids and primary alcohol concentrations over a large dynamic range with high sensitivity. Formic, acetic, and propionic acid were accurately determined at concentrations as low as 5 to 10 micrograms/L in under 20 minutes, or as high as 10 to 20 mg/L in under 30 minutes. Methanol, ethanol, and propanol were determined at concentrations as low as 20 to 100 micrograms/L, or as high as 10 mg/L in under 30 minutes. Importantly for space based application, the OAAM requires no reagents or hazardous chemicals to perform these analyses needing only power, water, and CO2 free purge gas. The OAAM utilized two membrane processes to segregate organic acids from interfering ions. The organic acid concentration was then determined based upon the conductiometric signal. Separation of individual organic acids was accomplished using a chromatographic column. Alcohols are determined in a similar manner after conversion to organic acids by sequential biocatalytic and catalytic oxidation steps. The OAAM was designed to allow the early diagnosis of under performing or failing sub-systems within the Water Recovery System (WRS) baselined for the International Space Station (ISS). To achieve this goal, several new technologies were developed over the course of the OAAM program.

Akse, James R.

Ambient cure polyimide foams prepared from aromatic polyisocyanates, aromatic polycarboxylic compounds, furfuryl alcohol, and a strong inorganic acid

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, e.g., pyromellitic dianhydride, with an aromatic polyisocyanate, e.g., polymethylene polyphenylisocyanate (PAPI) in the presence of an inorganic acid and a lower molecular weight alcohol, e.g., dilute sulfuric acid or phosphoric acid and furfuryl alcohol. The exothermic reaction between the acid and the alcohol provides the heat necessary for the other reactants to polymerize without the application of any external heat. Such mixtures, therefore, are ideally suited for in situ foam formation, especially where the application of heat is not practical or possible.

Sawko, Paul M.

Increased Dependence on Saccades for Ocular Tracking with Low Dose Alcohol

Previous studies have shown that certain features of oculomotor performance are impaired at or slightly below the legal limit for driving in most U.S. States (0.08% Blood Alcohol Concentration or BAC). Specifically, alcohol impairs saccadic velocity and steady-state tracking at levels between 0.04% and 0.1% BAC. Here we used a suite of standardized oculometric measures to examine the effect of ultra-low levels of alcohol (down to 0.01% BAC) on steady-state tracking. Our high-uncertainty tracking task reveals that the smooth pursuit system is highly sensitive to BAC, with impairmentextrapolating back to BAC levels at or below 0.01%. BAC generates a dose dependent increase in reliance on the saccadic system that maintains overall steady-state tracking effectiveness at least up to 0.08% BAC, albeit with a significant decrease in smoothness.

Tyson, Terence L.

High‐Concentration Alcohol Generation in Bipolar Membrane CO Electrolyzer

Electrochemical reduction of carbon dioxide and carbon monoxide offers an electricity‐powered route to make multicarbon liquid products. However, in conventional systems employing anion exchange membranes (AEMs), significant liquid product crossover leads to dilute product streams, increasing separation costs; and also produces unwanted anodic oxidation, further decreasing overall efficiency. Here, we report a forward‐biased bipolar membrane (FB‐BPM) system that achieves <10% liquid product crossover while sustaining a highly alkaline environment near the cathode, suppressing ethylene and hydrogen and favoring liquid products. By tuning catalyst composition to modulate the adsorption of *H and *OH, we steer selectivity toward acetate and alcohols. Using the FB‐BPM system, we achieve >25 wt% acetate on CuZn and >15 wt% alcohols on CuSn directly from the cathode outlet stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Properties and Autoignition Reactivity of Diesel Boiling Range Ethers Produced from Guerbet Alcohols

We examine the properties of diesel boiling range ethers made from coupling of alcohols produced by oligomerization of ethanol (Guerbet alcohols) for their utility as low-carbon liquid fuel blendstocks. Basic properties of boiling point, flash point, freezing point, density and viscosity are well suited for blending into diesel fuels. For the mixture of ethers the lightest component, di-n-butyl ether, can be present at up to 20 vol% while still having adequately high flashpoint for safe handling. Soot formation tendency (as yield sooting index) is well below that of conventional diesel. The ethers have similar compatibility with elastomers as conventional diesel, based on Hansen solubility parameter analysis. Oxidation stability was assessed for 30 vol% blends of individual ethers in a conventional diesel fuel using a long-term storage test. Over 6 weeks we observed no formation of peroxides or degradation. n-alkyl ethers with carbon number of 8 or higher have cetane number over 100, which is outside the defined range of cetane number, while branched ethers are over 70. The ethers also blend antagonistically into conventional diesel for cetane number, meaning that the blend cetane value is lower than predicted based on a linear by volume, mass, or mole model. We show that aromatics and naphthenes likely act as radical scavengers to slow or shut down autoignition of the highly reactive ethers at low to medium blend levels. Overall, diesel boiling range ethers show significant promise as high quality low-net carbon diesel blendstocks.

09 BIOMASS FUELS

Elucidating the Structural and Electronic Effects of Ni and Mn Cationic Incorporation on CoOOH for Efficient Benzyl Alcohol Electrooxidation

Transition-metal oxyhydroxides such as CoOOH are promising low-cost electrocatalysts for the selective electrooxidation of organic molecules, yet the influence of ubiquitous transition-metal impurities on their performance and durability remains poorly understood. Here, we experimentally probed the individual and synergistic electrochemical and structural effects of Ni and Mn incorporations into model CoOOH electrocatalysts toward an efficient benzyl alcohol oxidation reaction (BAOR). Comprehensive electrochemical, microscopic, and spectroscopic analyses reveal that Ni incorporation enhances charge-transfer kinetics and overall activity through the formation of catalytically active Ni 3+ sites, whereas Mn exhibited a more complex but interesting role. At the early stages of operation, Mn 4+ acts as a stabilizing surface layer that mitigates catalyst degradation but partially blocks Co sites before they undergo gradual leaching. The concurrent incorporation of both Ni and Mn yields a trimetallic 2NMC@NF electrocatalyst that integrates the activity benefits of Ni with the stability conferred by Mn, achieving 92.9% benzyl alcohol conversion and 91.4% Faradaic efficiency after 24 h at 1.5 V vs RHE. These findings elucidate how trace Ni and Mn impurities, often introduced from electrolytes or external sources, can modulate the lattice and electronic structure of CoOOH, offering a design strategy for enhancing both activity and long-term stability in electrocatalytic organic oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Epoxide Alcoholysis over M-BEA Zeolites: Effects of Alcohol Chain Length on Rates and Regioselectivities

The structures of nucleophilic reactants affect their coordination behavior among solvent molecules and kinetics of reactions with surface intermediates within the confines of fluidfilled pores of zeolites and other microporous materials. Consequently, rates and regioselectivities of diverse chemistries may depend sensitively on nucleophile identity in manners not observed for classic fluid phase reactions. Here, we examine the impact of varying the primary alcohol (ROH) chain length on the kinetics of 1,2-epoxybutane (C 4 H 8 O) ring-opening within Brønsted (Al-BEA) and Lewis acid (Zr-BEA) zeolites. Turnover rates increase by factors of ∼6 (Al-BEA) and 4-fold (Zr-BEA) between methanol and 1-hexanol, yet the reaction mechanisms remain comparable. Despite modest rate differences, apparent activation enthalpies calculated from rates and activities of solvated reactants decrease linearly by 12 (Al-BEA) to 33 kJ mol −1 (Zr- BEA) with increased proton affinity, which suggests bond formation energies for the nucleophile strongly influence rate increases. The molecular interpretation of these trends demonstrates, however, that the solvation of ring-opening transition states by zeolite pore structures and solvent molecules also governs rates. The impact of local solvating interactions appears most directly as changes in regioselectivities, which tend to enhance terminal alcohol formation with increasing ROH chain length. Regioselectivities largely do not vary with differences in fluid composition for a given ROH. The addition of H 2 O increases the number of hydrogen bonds among reactive species, and trends in regioselectivities imply that the decreased hydrogen bonding ability of longer chain ROH, and not the nucleophile strength or steric bulk, determines the regioselectivities of the resulting products. This work provides direct experimental evidence that nucleophilicity and hydrogen bonding influence reaction barriers and regioselectivities in zeolitecatalyzed epoxide ring-opening, offering pathways to better control reaction kinetics.

acidic zeolites

Illuminating the Role of Alcohol Substrate in Nickel Photoredox Catalysis via Ground State and Transient Absorption Spectroscopy

Direct excitation of nickel photocatalysts has gained popularity over the last several years following the successful activation of nickel by Ir and Ru photosensitizers. The ability to pair these photosensitizers with Ni catalysts facilitates the formation of crucial chemical bonds under relatively mild conditions. However, there are still gaps in our understanding of what influences the performance of these Ni photocatalysts. Previous work from our group identified a nickel photocatalyst supported by a tridentate pyridinophane ligand that undergoes wavelength-dependent cross-coupling reactivity. Herein, we report detailed studies of the wavelength dependence of the C–O cross-coupling reactivity, illustrating that the catalytic activity has an optimal wavelength, and excitation on both the blue and red sides of this optimal wavelength leads to a reduction in product yield. We also reveal a crucial catalyst-alcohol preirradiation interaction that drastically alters the catalyst’s optical properties. Furthermore, we investigate both wavelength dependency and alcohol dependency via optical transient absorption spectroscopy and reveal a substrate binding process responsible for the observed wavelength-dependent cross-coupling catalysis.

alcohol