939 resultados para Effect of water
Resumo:
Au catalysis has been one of the hottest topics in chemistry in the last 10 years or so. How O-2 is supplied and what role water plays in CO oxidation are the two challenging issues in the field at the moment. In this study, using density functional theory we show that these two issues are in fact related to each other. The following observations are revealed: (i) water that can dissociate readily into OH groups can facilitate O-2 adsorption on TiO2; (ii) the effect of OH group on the O-2 adsorption is surprisingly long-ranged; and (iii) O-2 can also diffuse along the channel of Ti (5c) atoms on TiO2(1 10), and this may well be the rate-limiting step for the CO oxidation. We provide direct evidence that O-2 is supplied by O-2 adsorption on TiO2 in the presence of OH and can diffuse to the interface of Au/TiO2 to participate in CO oxidation. Furthermore, the physical origin of the water effects on Au catalysis has been identified by electronic structure analyses: There is a charge transfer from TiO2 in the presence of OH to O-2, and the O-2 adsorption energy depends linearly on the 02 charge. These results are of importance to understand water effects in general in heterogeneous catalysis.
Resumo:
Water, one of the most popular species in our planet, can play a catalytic role in many reactions, including reactions in heterogeneous catalysis. In a recent experimental work, Bergeld, Kasemo, and Chakarov demonstrated that water is able to promote CO oxidation under low temperatures (similar to200 K). In this study, we choose CO oxidation on Pt(111) in the presence of water as a model system to address the catalytic role of water for surface reactions in general using density functional theory. Many elementary steps possibly involved in the CO oxidation on Pt(111) at low temperatures have been investigated. We find the following. First, in the presence of water, the CO oxidation barrier is reduced to 0.33 eV (without water the barrier is 0.80 eV). This barrier reduction is mainly due to the H-bonding between the H in the H2O and the O at the transition state (TS), which stabilizes the TS. Second, CO can readily react with OH with a barrier of 0.44 eV, while COOH dissociation to produce CO2 is not easy (the barrier is 1.02 eV). Third, in the H2O+OH mixed phase, CO can be easily converted into CO2. It occurs through two steps: CO reacts with OH, forming COOH; and COOH transfers the H to a nearby H2O and, at the same time, an H in the H2O transfers to a OH, leading to CO2 formation. The reaction barrier of this process is 0.60 eV under CO coverage of 1/6 ML and 0.33 eV under CO coverage of 1/3 ML. The mechanism of CO oxidation at low temperatures is discussed. On the basis of our calculations, we propose that the water promotion effect can in general be divided into two classes: (i) By H-bonding between the H of H2O and an electron negative species such as the O in the reaction of CO+O+H2O-->CO2+H2O, H2O can stabilize the TS of the reaction and hence reduce the barrier. (ii) H2O first dissociates into H and OH and then OH or H participates directly in the reaction to induce new reaction mechanism with more favorable routes, in which OH or H can act as an intermediate. (C) 2003 American Institute of Physics.
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There is an increasing need to identify the effect of mix composition on the rheological properties of composite cement pastes using simple tests to determine the fluidity, the cohesion and other mechanical properties of grouting applications such as compressive strength. This paper reviews statistical models developed using a fractional factorial design which was carried out to model the influence of key parameters on properties affecting the performance of composite cement paste. Such responses of fluidity included mini-slump, flow time using Marsh cone and cohesion measured by Lombardi plate meter and unit weight, and compressive strength at 3 d, 7 d and 28 d. The models are valid for mixes with 0.35 to 0.42 water-to-binder ratio (W/B), 10% to 40% of pulverised fuel ash (PFA) as replacement of cement by mass, 0.02 to 0.06% of viscosity enhancer admixture (VEA), by mass of binder, and 0.3 to 1.2% of superplasticizer (SP), by mass of binder. The derived models that enable the identification of underlying primary factors and their interactions that influence the modelled responses of composite cement paste are presented. Such parameters can be useful to reduce the test protocol needed for proportioning of composite cement paste. This paper attempts also to demonstrate the usefulness of the models to better understand trade-offs between parameters and compare the responses obtained from the various test methods which are highlighted. The multi parametric optimization is used in order to establish isoresponses for a desirability function of cement composite paste. Results indicate that the replacement of cement by PFA is compromising the early compressive strength and up 26%, the desirability function decreased.
Resumo:
The underwater casting of relatively thin lifts of concrete in water requires the proportioning of highly flowable concrete that can resist water dilution and segregation and spread readily into place. An investigation was carried out to determine the effects of antiwashout admixture concentration, water-cementitious materials ratio, and binder composition on the washout resistance of highly flowable concrete. Two main types of antiwashout admixtures were used: 1) a powdered welan gum at concentrations of 0.07 and 0.15% (by mass of binder); and 2) a liquid-based cellulosic admixture with dosages up to 1.65 L/100 kg of binder. The water-cementitious materials ratios were set at 0.41 and 0.47, corresponding to high-quality underwater concrete. Four binder compositions were used: a standard Canadian Type 10 cement, the same cement with 10% silica fume replacement, the cement with 50% granulated blast-furnace slag replacement, and a ternary cement containing 6% silica fume and 20% Class F fly ash. The concentrations of anti-washout admixture have direct impact on washout resistance. For a given washout loss, greater slump flow consistency can be achieved with the increases in anti-washout admixture concentration and decreases in water-binder ratio. The washout mass loss can be reduced, for a given consistency
Resumo:
Concrete used for underwater repair is often proportioned to spread readily into place and self-consolidate, and to develop high resistance to segregation and water dilution. An investigation was carried out to determine the effect of the dosage of antiwashout admixture, water-cementitious materials ratio (w/cm), and binder composition on the relative residual strength of highly flowable underwater concrete. Two types of antiwashout admixtures were used: a powdered welan gum at 0.07 and 0.15% by mass of binder, and a liquid-based cellulosic admixture employed at a high dosage of 1 to 1.65 L/100 kg of cementitious materials. The w/cms were set at 0.41 and 0.47 to secure adequate performance of underwater concrete for construction and repair. Four binder compositions were used: a Canadian Type 10 cement; a cement with 10% silica fume replacement; a cement with 50% replacement of granulated blast-furnace slag; and a ternary binder containing 6% silica fume and 20% Class F fly ash. Test results indicate that for a given washout mass loss and slump flow consistency, greater relative residual strength can be secured when the dosage of antiwashout admixture is increased, the w/cm is reduced, and a binary binder with 10% silica fume substitution or the ternary binder are employed. Such mixtures can develop relative residual compressive strengths of 85 and 80%, compared to mixtures cast in air, when the value of washout loss is limited to 4 and 6% for mixtures with slump flow values of 450 and 550 mm, respectively.
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We describe perfluoropolyether (PFPE) surfactants which are capable of stabilising the water/CO2 interface and present FTIR spectroscopic evidence for the formation of water in supercritical carbon dioxide microemulsions. A wide variety of single chain surfactants of differing chain lengths but similar structure has been screened and the effect of the surfactant chain length on the water uptake was studied. The ammonium carboxylate of the PFPE surfactant Krytox FSL(TM) with an average molecular weight of 2500 g mol(-1) was demonstrated to be the surfactant capable of dissolving the most water out of all the tested surfactants and hence to have the optimum chain length. (C) 2002 Elsevier Science B.V. All rights reserved.
Resumo:
DRIFTS, TGA and resistance measurements have been used to study the mechanism of water and hydrogen interaction accompanied by a resistance change (sensor signal) of blank and Pd doped SnO2. It was found that a highly hydroxylated surface of blank SnO2 reacts with gases through bridging hydroxyl groups, whereas the Pd doped materials interact with hydrogen and water through bridging oxygen. In the case of blank SnO2 the sensor signal maximum towards H-2 in dry air (R-0/R-g) is observed at similar to 345 degrees C, and towards water, at similar to 180 degrees C, which results in high selectivity to hydrogen in the presence of water vapors (minor humidity effect). In contrast, on doping with Pd the response to hydrogen in dry air and to water occurred in the same temperature region (ca. 140 degrees C) leading to low selectivity with a high effect of humidity. An increase in water concentration in the gas phase changes the hydrogen interaction mechanism of Pd doped materials, while that of blank SnO2 is unchanged. The interaction of hydrogen with the catalyst doped SnO2 occurs predominantly through hydroxyl groups when the volumetric concentration of water in the gas phase is higher than that of H-2 by a factor of 1000.
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The effect of blanching (95 ± 3 °C) followed by sous vide (SV) processing (90 °C for 10 min) on levels of two polyacetylenes in parsnip disks immediately after processing and during chill storage was studied and compared with the effect of water immersion (WI) processing (70 °C for 2 min.). Blanching had the greatest influence on the retention of polyacetylenes in sous vide processed parsnip disks resulting in significant decreases of 24.5 and 24% of falcarinol (1) and falcarindiol (2) respectively (p < 0.05). Subsequent SV processing did not result in additional significant losses in polyacetylenes compared to blanched samples. Subsequent anaerobic storage of SV processed samples resulted in a significant decrease in 1 levels (p < 0.05) although no change in 2 levels was observed (p > 0.05). 1 levels in WI processed samples were significantly higher than in SV samples (p = 0.05). 2 was particularly susceptible to aerobic storage following WI processing with losses of up to 70% occurring after 5 days storage. 1 type polyacetylene undergoes degradation such as oxidation, dehydrogenation when thermally treated forming oxidized form of 1 type molecules, in this case falcarindione, dehydrofalcarinol, dehydrofalcarinone. Thermal processing had a significant effect on instrumental color of parsnip samples compared to minimally processed in both SV and WI processed samples resulting in parsnip disks becoming darker, yellower and browner following processing and storage.
Resumo:
The structures of liquid water and isopropanol have been studied as a function of the size of a hydrophobic patch present in a model hydrophilic surface via molecular dynamics simulations. A significant anisotropy extending into the first few solvent layers is found over the patch which suggests implications for many real-world systems in which nanoscale heterogeneity is found.
Resumo:
Organic gels have been synthesized by sol–gel polycondensation of phenol (P) and formaldehyde (F) catalyzed by sodium carbonate (C). The effect of synthesis parameters such as phenol/catalyst ratio (P/C), solvent exchange liquid and drying method, on the porous structure of the gels have been investigated. The total and mesopore volumes of the PF gels increased with increasing P/C ratio in the range of P/C B 8, after this both properties started to decrease with P/C ratio for P/C[8 and the gel with P/C = 8 showed the highest total and mesopore volumes of 1.281 and 1.279 cm3 g-1 respectively. The gels prepared by freeze drying possessed significantly higher porosities than the vacuum dried gels. The pore volume and average pore diameter of the freeze dried gels were significantly higher than those of the vacuum dried gels. T-butanol emerged as the preferred solvent for the removal of water from the PF hydrogel prior to drying, as significantly higher pore volumes and specific surface areas were obtained in the corresponding dried gels. The results showed that freeze drying with t-butanol and lower P/C ratios were favourable conditions for the synthesis of highly mesoporous phenol–formaldehyde gels.
Resumo:
In this study, the feasibility of using H3PO4-activated lignin for hexavalent chromium adsorption has been investigated. The composite of activated lignin was characterized using FTIR, XRD and SEM with EDAX analysis. It was observed that the pH had a strong effect on the adsorption capacity; adsorption of Cr(VI) was more favorable at acidic pH with maximum uptake at pH 2. The adsorption equilibrium data were best represented by Koble-Corrigan isotherm. The monolayer sorption capacity obtained from the Langmuir model was found to be 77.85 mg/g. Adsorption showed pseudo-second order rate kinetics and the process involving the rate-controlling step is complex as it involves both film and intraparticle diffusion processes. The NaOH desorbing agent was able to release approximately 84% of metal ions. Thermodynamic parameters showed that the sorption process is exothermic and non-spontaneous. The overall Cr(VI) retention on the activated lignin surface perhaps includes both the physical adsorption of Cr(VI) and the consequent reduction of Cr(VI) to Cr(III). (C) 2011 Elsevier B.V. All rights reserved.
Resumo:
The effect of the addition of water on the absorption of carbon dioxide by the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide was studied experimentally by measuring the low-pressure carbon dioxide solubility and the viscosity of the liquid solvent at temperatures from 303 to 323 K. Water is only partially miscible with the ionic liquid up to a mole fraction of 0.302 at 293 K, 0.321 at 303 K and 0.381 at 323 K. It was observed that the solubility of carbon dioxide decreases with the quantity of water from a mole fraction of 2.63 × 10-2 for the pure ionic liquid at 303.4 K to a value of 1.88 × 10-2, a reduction of 30% of the solubility, for a mole fraction of water of 0.28. The viscosity of the liquid solvent also decreases, up to 40% at 303 K, from 28.6 mPa s for the pure ionic liquid to 16.4 mPa s for a water mole fraction of 0.302.
Resumo:
To meet European Union renewable energy and greenhouse gas emissions reduction targets the Irish government set a target in 2008 that 10% of all vehicles in the transport fleet be powered by electricity by 2020. Similar electric vehicle targets have been introduced in other countries. However, reducing energy consumption and decreasing greenhouse gas emissions in transport is a considerable challenge due to heavy reliance on fossil fuels. In fact, transport in the Republic of Ireland in 2009 accounted for 29% of non-emissions trading scheme greenhouse gas emissions, 32% of energy-related greenhouse gas emissions, 21% of total greenhouse gas emissions and approximately 50% of energy-related non-emission trading scheme greenhouse gas emissions. In this paper the effect of electric vehicle charging on the operation of the single wholesale electricity market for the Republic of Ireland and Northern Ireland is analysed. The energy consumed, greenhouse gas emissions generated and changes to the wholesale price of electricity under peak and off-peak charging scenarios are quantified and discussed. Results from the study show that off-peak charging is more beneficial than peak charging.