Gas-phase Concentrations Research Articles

Ultra-low concentration detection of dissolved C2H2 in oil using fixed-frequency RF-assisted calibration-free wavelength modulation spectroscopy

The monitoring sensitivity of dissolved C2H2 in transformer oil is crucial to ensuring the safe operation of electric power systems. A highly sensitive sensor system based on fixed-frequency radio frequency assisted calibration-free wavelength modulation spectroscopy (FF-RF-WMS-2f/1f) for dissolved C2H2 in transformer oil was developed and evaluated. Lowering the headspace sampling pressure to 0.1 atm effectively increased the outgassing ratio and detection signal of dissolved C2H2, while also reducing background interference. By employing a novel fixed-frequency RF-assisted modulation technique, we effectively suppressed the amplitude and influence of optical fringes and improved the system’s linear fitting R-squared value for gas-phase concentration from 0.9997 to 0.9999. Furthermore, the minimum detection limit (MDL), as calculated by Allan deviation, was reduced from 8.58 ppb to 4.36 ppb, while the optimal integration time increased slightly from 62 s to 79 s. The equivalent MDL for dissolved C2H2 reached 0.9 ppb. The comparative experiments showed that the error was less than 0.2 ppm or 8 %, the relative standard deviations (RSDs) of continuous measurement were less than 3 %, and the RSD at ultra-low concentration was less than 8 %. The experiments verified the high sensitivity and accuracy of the sensor system, making it suitable for ultra-low concentration dissolved C2H2 detection in transformer insulating oil.

Widespread occurrence of pesticides in low-income housing

BackgroundLow socioeconomic status (SES) residents living in social housing, which is subsidized by government or government-funded agencies, may have higher exposures to pesticides used in indoor residences since pesticides are applied due to structural deficiencies, poor maintenance, etc.ObjectiveTo estimate exposure of residents in low-SES social housing built in the 1970s to legacy and current-use pesticides and to investigate factors related to exposures.MethodsTwenty-eight particle-phase pesticides were measured in the indoor air of 46 units in seven low-income social housing, multi-unit residential buildings (MURBs) in Toronto, Canada using portable air cleaners deployed for 1 week in 2017. Pesticides analyzed were legacy and current use in the classes: organochlorines, organophosphates, pyrethroids, and strobilurins.ResultsAt least one pesticide was detected in 89% of the units with detection frequencies (DF) for individual pesticides of up to 50%, including legacy organochlorines and current-use pesticides. Current-use pyrethroids had the highest DF and concentrations, with the highest particle-phase concentration for pyrethrin I at 32,000 pg/m3. Heptachlor, restricted for use in Canada in 1985, had the highest estimated maximum total air (particle plus gas phase) concentration of 443,000 pg/m3. Heptachlor, lindane, endosulfan I, chlorothalonil, allethrin, and permethrin (except in one study) had higher concentrations than those measured in low-income residences reported elsewhere. In addition to the intentional use of pesticides to control pests and their use in building materials and paints, tobacco smoking was significantly correlated with the concentrations of five pesticides used on tobacco crops. The distribution of pesticides with high DF in individual buildings suggested that pest eradication programs by the building management and/or pesticide use by residents were the major sources of measured pesticides.ImpactLow-income social housing fills a much-needed demand, but the residences are prone to pest infestation and hence pesticide use. We found exposure to at least 1 of 28 particle-phase pesticides in 89% of all 46 units tested, with the highest DF and concentrations for current-use pyrethroids and long-banned organochlorines (e.g., DDT, heptachlor) due to very high persistence indoors. Also measured were several pesticides not registered for use indoors, e.g., strobilurins used to treat building materials and pesticides used on tobacco crops. These results, which are the first Canadian data for most pesticides indoors, show widespread exposure to numerous pesticides.

An improved multiphase chemistry mechanism for methylamines: significant dimethylamine cloud production

Monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA) are important compounds for atmospheric key processes, e.g., new particle formation (NPF). A description of their multiphase chemical processing within atmospheric models is incomplete, but mandatory to describe their atmospheric budgets. In this study, a detailed multiphase chemistry mechanism was developed and first process model investigations were performed. The simulations focused on pristine marine conditions, where open research questions exist regarding ambient gas-phase concentrations of methylamines, particularly with regards to unexpectedly high DMA levels. The simulations reveal that TMA oxidation in cloud droplets results into DMA formation with a yield of around 87%, a missing DMA production pathway in current models. Also, it is demonstrated that about 21% and 69% of the respective DMA and TMA gas-phase oxidation proceed via autoxidation yielding HOOCH2NHCHO and HOOCH2N(CHO)CH2OOH, respectively. The discussed processes should be included into atmospheric models for advanced predictions of NPF and climate impacts.

Investigation on flow structure and pressure fluctuation of gas-liquid two-phase flow in a mixed flow pump

Abstract Mixed flow pump is characterized by high-efficiency operation and wide range of flow rate conditions, while research on transporting gas-liquid two-phase flow is quite limited. The present work investigates the energy performance, two-phase flow pattern and pressure fluctuations of a mixed flow pump, on basis of the numerical method of inhomogeneous Eulerian-Eulerian multiphase flow model. Results show that the pump head and efficiency decline with the increase of gas volume fraction. In impeller, gas phase is mainly distributed at the tip clearance, the blade pressure side and suction side, and the hub outlet. The low pressure of tip leakage vortex core leads to the gas phase concentration and the formation of gas strip. Moreover, X-shaped gas strip appears at high gas volume fraction (GVF). In guide vane, gas phase is mainly distributed at the leading edge of blade pressure side, the blade suction side, and the middle of passage. As the inlet GVF increases, the spatial-temporal evolution of the gas phase shows obvious differences. The strong gas-liquid interaction causes broad low-frequency fluctuations, and the rotor-stator interference causes significant blade passing frequencies in the mixed flow pump.

Urban air PCDD/Fs: Atmospheric concentrations, temporal changes, gas/particle partitioning, possible sources and cancer risks

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) are pollutants of concern due to their toxic effects. No active sampling study on PCDD/Fs has been conducted in Bursa. This study aimed to fill this gap by measuring PCDD/F levels in the region. Accordingly, the samples were collected from an urban area in Bursa, covering four seasons between June 2022 and April 2023. The total (gas+particulate) ambient air concentrations were between 312.23 and 829.80 fg/m3 (mean: 555.05 ± 173.62 fg/m3). In terms of toxic equivalents (TEQ), the average concentration was 43.29 ± 9.18 fg WHOTEQ/m3. Based on the concentration values obtained, cancer and non-carcinogenic risk values of PCDD/Fs were calculated for three different age groups. The results indicated negligible health risks for all age groups. In addition, a seasonal assessment was also made and it was observed that PCDD/F concentration values varied with the ambient air temperatures. In general, higher values were measured in colder months compared to warmer months. This was probably due to the additional sources and adverse meteorological conditions. Moreover, the gas/particle partitioning of PCDD/Fs was investigated in detail. The average gas and particulate phase concentrations for PCDD/Fs were 101.81 ± 20.77 and 453.24 ± 172.50, respectively. It was found that an equilibrium state was not reached in the gas/particle partitioning. Two different gas/particle partition models based on adsorption and absorption mechanisms were compared, and the absorption model gave more consistent predictions. The Principal Component Analysis (PCA) was employed to identify the possible PCDD/F sources. The results indicated that the region was influenced by vehicle emissions, residential heating, organized industrial zones and metal recycling facilities. In addition, 72-hour backward air mass trajectory analyses were performed to understand the long-range transported air masses. However, it was found that the transported air masses did not significantly affect the concentration values measured in the sampling site.

Simultaneous time-resolved inorganic haloamine measurements enable analysis of disinfectant degradation kinetics and by-product formation.

We demonstrate the application of proton transfer time-of-flight mass spectrometry (PTR-TOF-MS) in monitoring the kinetics of disinfectant decay in water with a sensitivity one to three orders of magnitude greater than other analytical methods. Chemical disinfection inactivates pathogens during water treatment and prevents regrowth as water is conveyed in distribution system pipes, but it also causes formation of toxic disinfection by-products. Analytical limits have hindered kinetic models, which aid in ensuring water quality and protecting public health by predicting disinfection by-products formation. PTR-TOF-MS, designed for measuring gas phase concentrations of organic compounds, was able to simultaneously monitor aqueous concentrations of five inorganic haloamines relevant to chloramine disinfection under drinking water relevant concentrations. This novel application to aqueous analytes opens a new range of applications for PTR-TOF-MS.

A Surface Hydrothermal Source of Nitriles and Isonitriles.

Giant impacts can generate transient hydrogen-rich atmospheres, reducing atmospheric carbon. The reduced carbon will form hazes that rain out onto the surface and can become incorporated into the crust. Once heated, a large fraction of the carbon is converted into graphite. The result is that local regions of the Hadean crust were plausibly saturated with graphite. We explore the consequences of such a crust for a prebiotic surface hydrothermal vent scenario. We model a surface vent fed by nitrogen-rich volcanic gas from high-temperature magmas passing through graphite-saturated crust. We consider this occurring at pressures of 1-1000bar and temperatures of 1500-1700 ∘C. The equilibrium with graphite purifies the leftover gas, resulting in substantial quantities of nitriles (0.1% HCN and 1ppm HC3N) and isonitriles (0.01% HNC) relevant for prebiotic chemistry. We use these results to predict gas-phase concentrations of methyl isocyanide of ∼1 ppm. Methyl isocyanide can participate in the non-enzymatic activation and ligation of the monomeric building blocks of life, and surface or shallow hydrothermal environments provide its only known equilibrium geochemical source.

Smartphone-Based Color Evaluation of Passive Samplers for Gases: A Review

The application of smartphone-based color evaluation of passive sampling devices for gases has only been sparsely reported. The present review aims to compile available publications with respect to the configuration of the passive samplers, conditions of smartphone photographing, analytical procedures for color detection and quantification (including calibration processes), and their application to different target gases. The performance of the methods—whenever available—is presented regarding the analytical specifications selectivity, sensitivity, and limit of detection in comparison with other color evaluation methods of passive samplers. Practical aspects like requirements of instrumentation and ease of use will be outlined in view of the potential employment in education and citizen science projects. In one section of the review, the inconsistent terminology of passive and diffusive sampling is discussed in order to clarify the distinction of information obtained from the uptake of the passive samplers between gas-phase concentration and the accumulated deposition flux of gaseous analytes. Colorimetric gas sensors are included in the review when applied in passive sampling configurations and evaluation is performed with smartphone-based color evaluation. Differences in the analytical procedures employed after the passive sampling step and prior to the detection of the colored compounds are also presented.

Dust phase and window film phase phthalates in dormitories: profile characteristics, source screening, and estimated gas-phase concentration and dermal exposure comparison.

Recently, phthalate exposure has become a major public health concern. However, gaps still remain in our understanding of phthalate profile characteristics, source screening, and gas-phase estimation. This study measured phthalate concentrations in dust and window films in 101 dormitories at 13 universities in Beijing, China, from October to December 2019. Based on the phthalate concentrations in the dust and window films, we estimated the gas-phase phthalate concentrations using steady-state and instantaneous equilibrium models, respectively, and male and female students' dermal exposure using the Monte Carlo simulation. Commonly used materials and supplies were screened for phthalate sources and evaluated using the positive matrix factorization (PMF) model. The results showed that the detection frequency of ten phthalates ranged from 79.2 to 100% in dust and from 84.2 to 100% in window films. Dicyclohexyl phthalate (DCHP), di-(2-ethylhexyl) phthalate (DEHP), and dibutyl phthalate (DBP) were the most abundant phthalates in both indoor media and were also predominant in the indoor materials and supplies. The PMF results indicated that the potential sources of phthalates in dust and window films had both similarities and differences. Indoor door seals, paint, coatings, cables, air-conditioning rubber cable ties, wallpaper, and window seals were highly probable sources of phthalates. The gas-phase phthalate concentrations estimated using the two methods differed, especially for phthalates with high octanol-air partition coefficients (Koa), varying by 1-2 orders of magnitude. Moreover, compared with related studies, the gas-phase concentrations were significantly underestimated for phthalates with high Koa values, while the estimated gas-phase concentrations of phthalates with low Koa values were closer to the measured values. The estimated dermal exposure using the two methodologies also considerably differed. Such findings suggest that more attention should be focused on the exposure risk from the dust phase and window film phase phthalates.

Exposure assessment during paint spraying and drying using PTR-ToF-MS.

Spraying is a common way to distribute occupational products, but it puts worker's health at risk by exposing them to potentially harmful particles and gases. The objective of this study is to use time-resolved measurements to gain an understanding of spray applications at the process level and to compare them to predictions of exposure models. We used proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) at 1-s time resolution to monitor the gas phase concentration of the solvents acetone, ethanol, butyl acetate, xylene and 1-methoxy-2-propy acetate during outdoor spraying and indoor drying of metal plate under various conditions of outdoor air supply. We found that during spraying, gas-phase exposure was dominated by the more volatile solvents acetone and ethanol, which exhibited strong concentration variations due to the outdoor winds. During drying, exposure strongly depended on the strength of ventilation. Under conditions with high supply of outdoor air, our measurements show a near-exponential decay of the solvent concentrations during drying. Conversely, under conditions without outdoor air supply, the drying process required hours, during which the less volatile solvents passed through a concentration maximum in the gas phase, so that the exposure during drying exceeded the exposure during spraying. The concentrations measured during spraying were then compared for each of the substances individually with the predictions of the exposure models ECETOC TRA, Stoffenmanager, and ART using TREXMO. For these conditions, ECETOC TRA and Stoffenmanager predicted exposures in the measured concentration range, albeit not conservative for all solvents and each application. In contrast, ART largely overestimated the exposure for the more volatile solvents acetone and ethanol and slightly underestimated exposure to 1M2PA for one spraying. ECETOC TRA and ART do not have options to predict exposure during drying. Stoffenmanager has the option to predict drying together with spraying, but not to predict the drying phase independently. Our study demonstrates the importance of considering both the spray cloud and solvent evaporation during the drying process. To improve workplace safety, there is a critical need for enhanced exposure models and comprehensive datasets for calibration and validation covering a broader range of exposure situations.

Full-field vapor concentration and temperature field measurement of an evaporating ethanol–water binary sessile drop by tomographic laser absorption spectroscopy

Quantitative measurement of full-field, spatially resolved temperature and concentration field of pure water and ethanol–water binary evaporating drop is realized, in which the gas-phase and interfacial temperature and concentration are accurately captured. By studying the vapor field of evaporating drop under different heating temperatures, it is demonstrated that the method can achieve a spatial resolution below 100 μm and a time resolution of <10 s. Simultaneous gas-phase temperature and concentration field measurements reveal the occurrence of buoyancy convection in the gas phase. Through the analysis of interfacial temperature and concentration distribution, it is observed that in the process of pure water drop evaporation, both buoyancy-driven convection and thermal Marangoni convection exist, while in the ethanol–water binary drop evaporation, the solutal Marangoni flow convection and thermal Marangoni convection are coupled, and the buoyancy convection is suppressed. The interfacial temperature and gas-phase water vapor concentration can be obtained from the water vapor measurement, and combined with the activity coefficient models. The liquid-phase mole fraction of water at the interface and its distribution are also obtained, such that the liquid-phase mole fraction distribution of ethanol at the interface can be obtained, and finally, the concentration of ethanol vapor near the interface is obtained. The full-field, high-resolution measurement of evaporated drops is of substantial significance for in-depth understanding of the evaporation process. The measurement of ethanol–water binary drop evaporation provides a new research perception and method exploiting the spectral dimension, providing both quantitative and qualitative observations for the study of multi-component drop evaporation.

Multi-line OH-LIF for gas-phase temperature and concentration imaging in the SpraySyn burner

Gas-phase temperature and OH concentration images are measured in the SpraySyn nanoparticle-synthesis standard burner using multi-line OH laser-induced fluorescence (LIF) thermometry. In this burner, a spray flame fed by a combustible nanoparticle precursor solution is stabilized by a surrounding axisymmetric lean premixed laminar methane/oxygen pilot flame. For measuring OH rotational temperature, the laser is scanned across the 282.05–282.17 nm range and LIF excitation spectra are fitted for each image pixel by simulated spectra. Temperature maps are determined for the pilot flame and the ethanol spray flame with variable dispersion gas flow rates of oxygen used in the two-fluid nozzle. The addition of 2-EHA (2-ethylhexanoic acid) to the solution was found to increase the flame temperature. Laser attenuation across the flame was measured using simultaneous recordings of the fluorescence of uranine/water solution from two dye cuvettes illuminated with the laser sheet before and after the flame and the effect of attenuation was quantified. Absolute OH concentration distributions are determined by combining the LIF images, laser attenuation measurements, and derived temperature distributions. The temporal stability of the flame is investigated for various operating conditions by statistical evaluation of recorded instantaneous OH-LIF images.

Recommendations for improving the experimental protocol for the determination of photocatalytic activity by nitric oxide oxidation measurements.

The photocatalytic nitric oxide (NO) oxidation reaction is used as a standard diagnostic tool for photocatalytic activity according to the well-defined protocol described by ISO Standard 22197-1-2007. This protocol identifies the negative peak showing a NOx concentration drop during a gas flow switch from the calibration bypass to the reactor as adsorption of NOx on the surface. Evidence is provided for this first transient to be due to a dilution effect in the gas phase within the reactor. With proper models of residence time distribution analysis, this transient revealed the internal hydrodynamics and it can be used to determine the internal volumes of the system. The second transient occurs immediately after the light is switched on. The conversions strongly depend on the time constant of this transient. Controlled measurements of the effect of illumination intensity revealed that at higher light intensities the transient takes longer to reach steady state. The longer transient was attributed to the time needed to reach a thermal steady state of the hot spots generated by the recombination of excess charge carriers. When the catalyst amount was investigated as a parameter, a saturation effect was observed. This saturation effect was correlated with the gas phase concentrations of NOx and moisture and their ratios to the available specific surface area. Hence, additional constraints with respect to the illumination intensity and catalyst amounts are recommended for accurate measurements of photocatalytic activity by NO oxidation.

Periodic states and their implications in gas hydrate systems

Gas hydrates are one of the largest marine carbon reservoirs on Earth. The conventional understanding of hydrate dynamics assumes that the system, in the absence of external triggers, converges to a steady-state over geological time-scales, achieving fixed concentrations of gas hydrate and free gas phase. However, using a high-fidelity numerical model and consistently resolving phase states across multiple fluid-fluid and fluid-solid phase boundaries, we have identified well-defined periodic states embedded within hydrate system dynamics. These states lead to cyclic formation and dissolution of massive hydrate layers that is self-sustaining for the majority of natural marine settings. This previously unresolved characteristic could manifest as spontaneous gas migration and pressure release in, supposedly, unperturbed systems. Our findings show that the gas hydrate systems are not bound to have unique steady-state solutions. Instead, existence of periodic states introduces an irreducible, but, quantifiable uncertainty in gas hydrate dynamics which adds significant error bars to global gas hydrate inventory estimates.

Influence of Rotation Speed and Gas Content on the Transient Gas–Liquid Two-Phase Flow of an Electric Submersible Pump

In order to study the internal flow characteristics of the electric submersible pump (ESP) when the gas–liquid two-phase flow is conveyed by the variable frequency variable speed operation and the change of the imported gas content, the impeller of the Q10# ESP is taken as the research object, based on the Eulerian-Eulerian non-homogeneous phase. The flow model, the unsteady Reynolds time-averaged N-S equation, and the standard k-ε turbulence model are used for transient simulation calculations of the gas–liquid two-phase flow in the impeller of the ESP. Calculations show that with the rotation of the impeller, the gas phase is unevenly distributed in the flow channel. The gas phase is mainly concentrated on the inlet side of the flow channel near the front cover, and the gas phase exhibits periodic aggregation and diffusion in the flow channel. When the impeller speed increases, the period of periodic accumulation and diffusion of gas in the flow channel is shortened and the gas concentration in the impeller decreases, the overall flow velocity in the flow channel increases, and the pressure difference between the inlet and outlet increases. The pressure difference between the two sides of the blade is proportional to the speed of the impeller, and the fluctuation frequency of the blade surface also increases. As the gas content increases, the maximum concentration of gas phase in the flow channel increases. The area occupied by the high concentration of gas phase in the flow channel expands toward the blade’s working surface, and periodically accumulates, diffuses, and grows. The gas-liquid splitting area shrinks toward the front cover side and the pump. The internal pressure increases slightly, the main flow velocity increases, and the vortex action range increases.

Influence of reactor composition on the thermal decomposition of perfluorooctanesulfonic acid (PFOS)

Various reactor tubes (quartz, stainless steel 316 and stainless steel 253 MA) were used to examine their influence on the thermal decomposition of perfluorooctanesulfonic acid (PFOS) between 400 and 1000 °C. Using helium as a carrier gas, with the addition of 100 – 300 ppm of PFOS to the feed gas, the influence of the reactor materials on PFOS decomposition was studied. The quartz reactor led to a notable reduction in the concentration of HF and substantial quantities of SiF4 were observed. Stainless steel 316 produced C2F4, HF, COF2 and SO2 as its primary products up to 800 °C. However, at temperatures above 800 °C, near quantitative removal of SO2 from the gas phase was observed, with the concomitant formation of a blue molybdenum sulfur complex. Stainless steel 253 MA, the composition of which contains over 1% Si produced substantial quantities of SiF4 but no significant decrease in the gas phase concentration of HF. Environmental implicationThis research underscores the significant role of reactor material in the thermal treatment of PFAS, a globally widespread and enduring environmental contaminant. The findings have direct implications for the optimization of thermal treatment strategies aimed at mitigating PFAS contamination. The insight into how different reactor materials interact with PFOS during thermal treatment expands our understanding of potential destruction methods. This knowledge is crucial in the development of effective, sustainable strategies for managing persistent environmental pollutants like PFAS.

Simulation of Rayleigh convection during dichloromethane absorption by water using lattice Boltzmann method

Developing dichloromethane (DCM) waste gas purification and absorption technology is consistent with the demand of the circular economy and contributes to the goals of achieving carbon peaking and carbon neutrality. In addition, Rayleigh convection generated during the absorption of DCM by water is of great significance for understanding the interfacial mass transfer mechanism and enhancing the mass transfer efficiency. Thus, the absorption process of DCM discrete diffusion sources was simulated using the two-dimensional lattice Boltzmann method (LBM) with external forces to visualize the effect of Rayleigh convection evolution law on the mass transfer of the absorption process in this study. The concentration and velocity distribution with single or multiple diffusion sources were respectively simulated at 298.15 K and 1.00 atm. The results show that the convection structure of the simulated plume is similar to that of comparable studies, and the convective structure on both sides suppresses the development of the intermediate convective structure when convection occurs. At a constant gas-phase concentration (CB,g), the more the number of diffusion sources, the faster the convective structures integration, and the rapid integration of convective structures is associated with the sharp increasing instantaneous mass transfer flux. Meanwhile, increasing the gas phase concentration can effectively shorten the convection onset time (tc), increase the instantaneous mass transfer flux (Nins,t), and enhance the mass transfer efficiency by calculating the simulated transfer mass data. Furthermore, the critical onset time of Rayleigh convection first lengthens and then shortens with the number of diffusion sources (n) increasing. And the more the number of diffusion sources, the more significant the final cumulative (Nt) absorption amounts are. The simulation results can provide theoretical guidance for enhancing the mass transfer efficiency in the DCM absorption process.

Attraction of Frankliniella occidentalis Females towards the Aggregation Pheromone Neryl (S)-2-Methylbutanoate and Kairomones in a Y-Olfactometer.

An understanding of insect olfaction allows for more specific alternative methods of pest control. We evaluated the responses of the western flower thrips (WFT, Frankliniella occidentalis) in a Y-olfactometer to estimate gas-phase concentrations of the aggregation pheromone neryl (S)-2-methylbutanoate and known kairomones such as methyl isonicotinate, (S)-(-)-verbenone, and p-anisaldehyde. The gas-phase concentrations of these compounds were obtained from the release rates measured in dynamic headspace cells. The compounds were collected from the headspace using dried solid-phase extraction (SPE) cartridges and analyzed with a triple quadrupole GC-MS/MS. We observed that the aggregation pheromone significantly attracted WFT females at doses of 10 and 100 µg, whereas methyl isonicotinate and p-anisaldehyde significantly attracted WFT females at the highest dose. Verbenone did not produce any significant results. A completely different picture was obtained when the gas-phase concentrations were considered. The minimal gas-phase concentrations of the pheromone required to attract WFT females was 0.027 ng/mL, at least 100 times lower than that of the other two compounds. The relevance and implications of our results are discussed in light of the insect's biology and pest management methods.

Study of the photocatalytic reforming and oxidation of Glycerol over Ag–Pd/TiO2

The photocatalytic reaction of glycerol was conducted over 0.1 at. % Ag – 0.3 at.% Pd/TiO2 catalyst in order to monitor the switch over between the photo-reforming to hydrogen and CO2 and photo-oxidation to H2O and CO2. This alloy of Ag–Pd has shown to be more active than Pd for hydrogen ion reduction previously. Up to a partial pressure of about 0.2 atm. of molecular oxygen the rates of hydrogen production were mostly unaffected. There seems to be a threshold for the effect of O2 on the inhibition of hydrogen production. This is found when the ratio of dissolved molecular oxygen to surface Ti cations is about 2. Also, the order of reaction with respect to PO2 was found to be −2. Hydrogen production was found to be largely insensitive to glycerol concentrations (above 0.05 vol %) as expected from a zero order reaction kinetics in the liquid phase, where the rate is determined by surface coverage. The considerable amounts of dissolved CO2 found indicate that monitoring gas phase CO2 is not a true measurement of the photo-reaction rates. The dissolved CO2 concentration was 15–20% of the gas phase concentration of CO2 at any reaction time investigated. The fast decrease of the pH of the aqueous solution within the first 30 min points to the build up of oxidation products of glycerol. Liquid phase analysis showed the presence of formaldehyde, hydroxy acetone and ethylene glycol as the main reaction products. At high glycerol concentration the main product in the liquid phase was hydroxy acetone while at low concentrations it was formaldehyde. At low glycerol concentrations, the rise of formaldehyde concertation in the liquid phase with time was concomitant with hydrogen production, its decay with time, however, was not accompanied by further increase in hydrogen production. This is most likely because of the competition between decomposition in the presence of water (to H2 and CO2) and oxidation (to formates).

Generation and Observation of Long-Lasting and Self-Sustaining Marangoni Flow.

When solute molecules in a liquid evaporate at the surface, concentration gradients can lead to surface tension gradients and provoke fluid convection at the interface, a phenomenon commonly known as the Marangoni effect. Here, we demonstrate that minute quantities of ethanol in concentrated sodium hydroxide solution can induce pronounced and long-lasting Marangoni flow upon evaporation at room temperature. By employing particle image velocimetry and gravimetric analysis, we show that the mean interfacial speed of the evaporating solution sensitively increases with the evaporation rate for ethanol concentrations lower than 0.5 mol %. Placing impermeable objects near the liquid-gas interface enforces steady concentration gradients, thereby promoting the formation of stationary flows. This allows for contact-free control of the flow pattern as well as its modification by altering the objects shape. Analysis of bulk flows reveals that the energy of evaporation in the case of stationary flows is converted to kinetic fluid energy with high efficiency, but reducing the sodium hydroxide concentration drastically suppresses the observed effect to the point where flows become entirely absent. Investigating the properties of concentrated sodium hydroxide solution suggests that ethanol dissolution in the bulk is strongly limited. At the surface, however, the co-solvent is efficiently stored, enabling rapid adsorption or desorption of the alcohol depending on its concentration in the adjacent gas phase. This facilitates the generation of large surface tension gradients and, in combination with the perpetual replenishment of the surface ethanol concentration by bulk convection, to the generation of long-lasting, self-sustaining flows.