Equilibrium Vapor Research Articles

An Approximate Criterion for Morphological Transformations in Small Vapor Grown Ice Crystals

Abstract Observations and measurements show that crystals remain relatively compact at low ice supersaturations, but become increasingly hollowed and complex as the ice supersaturation rises. Prior measurements at temperatures >−25°C indicate that the transition from compact, solid ice to morphologically complex crystals occurs when the excess vapor density exceeds a threshold value of about 0.05 g m−3. A comparable threshold is not available at low temperatures. A temperature-dependent criterion for the excess vapor density threshold (Δρthr) that defines morphological transformations to complex ice is derived from laboratory measurements of vapor grown ice at temperatures below −40°C. This criterion depends on the difference between the equilibrium vapor density of liquid () and ice (ρei) multiplied by a measurement-determined constant, . The new criterion is consistent with prior laboratory measurements, theoretical estimates, and it reproduces the classical result of about 0.05 g m−3 above −25°C. Since Δρthr defines the excess vapor density above which crystals transition to a morphologically complex (lower density) growth mode, we can estimate the critical supersaturation (scrit) for step nucleation during vapor growth. The derived values of scrit are consistent with previous measurements at temperatures above −20°C. No direct measurements of scrit are available for temperatures below −40°C; however, our derived values suggest some measurement-based estimates may be too high while estimates from molecular dynamics simulations may be too low.

Structural evolutions of MX80 bentonite pellet/powder mixtures under wetting and suction-controlled oedometer loading

The compression behaviour of MX80 bentonite pellet/powder mixture was investigated by performing suction-controlled oedometer tests. The suction from 113 to 4.2 MPa was imposed by vapour equilibrium technique (VET), and zero suction by water circulation (WC). After instantaneously unloaded from various target vertical stresses, the structural observation was conducted by mercury intrusion porosimetry and micro-computed tomography. Results showed that during wetting, the intra-grain micro- and macro-pores increased due to the swelling of pellets and powder grains. During loading, the variation of intra-grain micro-pores was characterised by the loading effect, while that of intra-grain micro-pores was controlled by the suction and loading effects. The inter-grain pores, for the VET samples, were reduced by the swelling of pellets and powder grains during wetting on one hand, and by the movement of pellets and powder grains during loading on the other hand. For the WC samples, most inter-grain pores were closed during wetting, with a few pores in the top closed by further loading. The global compression of bentonite mixture samples during loading was mainly governed by the filling of inter-grain pores for the VET samples, but controlled by the compression of intra-grain pores for the WC samples.

Gas Chromatographic Determination of Residual Concentrations of a Mixture of Organochlorine Pesticides in Food Products

Purpose of research. The aim of the work is to optimize the conditions for gas chromatographic determination of a mixture of eight organochlorine pesticides: aldrin, hexachlorobenzene, heptachlor, α-hexachlorocyclohexane, γ-hexachlorocyclohexane, dichlorodiphenyltrichloromethylmethane, dichlorodiphenyldichloroethane and dichlorodiphenyldichloroethylene.Methods. For chromatographic studies of organochlorine pesticides we used a Shimadzu GC-2010Plus gas chromatograph (Shimadzu, Japan) equipped with an automatic equilibrium vapor sample dispenser NT200N, electron-capture detector based on 63Ni and quartz capillary nonpolar column "Chromatek" SPB-5 (30 m, 0.32 mm, film thickness on the basis of phenyl(5%) and dimethyl(95%) polysiloxanes 0.5 μm) with an operating temperature range of 60°C 320/340°C. The chromatograms were processed in the application LabSolutions GPC.Results. On the basis of experimentally obtained data the optimal conditions for gas chromatographic determination and separation of eight-component mixture of organochlorine pesticides were selected, namely: the value of mobile phase flow division 1:10, carrier gas flow rate – 1.0 ml/min, two-stage temperature programmable column mode from 160 to 240°C with the rate of increase of 5°C/min. The metrological characteristics of the analysis and validation of the results of the proposed technique with the method of high-performance liquid chromatography were evaluated. Good reproducibility of chromatography results with the possibility of detection of organochlorine pesticides at the level of 10-6 – 10-5 μg/cm3 was proved. Application of Fisher's test has shown absence of significant differences in reproducibility of sampled populations the investigated methods of chromatographic analysis of COPCs are equally accurate. Extraction sample preparation of samples of real objects was proposed, the calculated extraction degrees >84% allow to recommend the technique for quantitative determination of analytes.Conclusion. The method of gas chromatographic analysis was tested for determination of organochlorine pesticides in samples of drinking water and baby puree (Russia) by additive method. Exceeding the norms of residual contents of organochlorine pesticides in the samples of the food products under study was not detected.

Influences of ink-bottle effect evolution on water retention hysteresis of unsaturated soils: An experimental investigation

The ink-bottle effect, resulting from the non-uniformity of pore structure, plays a significant role in the hydraulic behaviour of soils. In this paper, a series of laboratory tests including standard mercury intrusion porosimetry (MIP), intrusion-extrusion cyclic MIP (IEC-MIP), and scanning electron microscopy (SEM) were conducted on two soils (a Nanyang expansive clay and a Kaolin mixture) to examine the evolution pattern of ink-bottle effect in soils with different initial void ratios. To evaluate the impact of such evolution on the soil-water retention behaviour, the axis translation and vapour equilibrium techniques were utilised to measure the water retention curve of the tested soils (SWRC). A key part of the analysis involved a separation between pore bodies (or ink-bottle pores) and pore throats to facilitate a more thorough examination of the pore structure. The test results indicated that the reduction in soil volume during compression is mainly attributed to the reduction in pore body size, whereas the pore throat size remains relatively constant. Therefore, the ink-bottle effect would weaken with a decreasing initial void ratio, which will reduce the hysteresis potential of soils, manifesting as a contraction of the SWRC hysteresis loop. Additionally, under a fixed void ratio but with decreasing pore size, the ink-bottle effect will also weaken, which will reduce the distance between the drying and wetting curves with increasing matric suction. Finally, the mechanisms regarding how the evolution of ink-bottle effect during soil deformation influences water retention hysteresis were addressed.

Experimental and modeling study of shear strength of unsaturated fine-grained soils with bi-modal water-retention characteristics

The mechanical behavior and strength characteristics of unsaturated fine-grained soils with dual-porosity are of crucial importance in geotechnical designs. Nanyang fine-grained soils have been selected as typical dual-porosity structure soils to perform experimental tests under a wide range of suction and different initial densities while studying its stress-strain-strength properties constitute the main scope of this study. Axial translation and vapor equilibrium techniques are jointly employed to apply a wide suction range. Our data suggest that soil behavior transits from strain-hardening with shear-induced contraction to strain-softening with shear-induced dilation as suction and density increase. By exploiting a bi-modal soil–water retention curve (SWRC) explicitly separating capillarity and adsorption mechanisms, the shear strength is allowed to be analyzed in the capillary suction stress-shear stress space. The strength envelop exhibits bi-linear characteristics. Building upon these findings, we propose a bi-linear shear strength criterion specifically for dual-porosity fine-grained soils. We utilize the obtained test data to evaluate existing strength criteria based on effective stress and dual stress variables that consider the bi-modal SWRC characteristics. The comparison indicates that the proposed bi-linear shear strength criterion can more reasonably represent the variation of shear strength under a wide range of suction for unsaturated dual-porosity fine-grained soils.

Study on the Effect of Soil Type and Salinity on Water–Soil Characteristic Curves of Saline Soils Based on the Vapor Balance Technique

The soil–water characteristic curve (SWCC) describes the relationship between water content and soil suction, which is an important tool for determining the engineering properties of unsaturated soil. By measuring SWCC through vapor equilibrium technique, which could obtain soil suction up to 309 MPa, this paper explored the influences of the soil type and salt content on SWCC of saline soil. The experimental results illustrate that fine‐grained saline soil had a good water‐holding capacity, which had a higher air entry value and slower dehydrate rate. The study also brings out the observation that salt had negligible influence on soil suction and parameters effecting SWCC in low suction range; however, this effects was slight until it disappeared with the suction increasing.

Recognition of supercritical CO2 liquid-like and gas-like molecules based on deep neural network

So far, it is still controversial about how to divide the liquid-like and gas-like states boundary and Widom delta, since the deviation of boundaries determined by different thermodynamic criteria increases significantly when away from the critical point. For this reason, a superior method that does not rely on thermodynamic criteria to define the boundary line between liquid-like and gas-like states needs to be proposed urgently and the recent extensive use of deep neural networks in molecular dynamics simulation provides a feasible choice. The present work attempts to determine a novel phase state boundary and Widom delta of supercritical CO2 from extracting the microstructure features of subcritical vapor and liquid states in equilibrium by deep neural network coupled with molecular dynamics simulation. In addition, visualization of simulated systems containing distinct liquid-like molecule ratio πLL of supercritical CO2 is also presented as well as the radial distribution function at different states. The results show that the novel boundary is located in the middle of the Widom lines constructed by multiple thermodynamic criteria. The lower boundary T- of the novel Widom delta agrees well with the theoretical boundary constructed by pseudo-boiling theory when it is close to the critical point but starts to deviate when it is far away from the critical point, while the upper boundary T+ of that is opposite. More importantly, the novel boundary and Widom delta constructed have no pressure upper limit compared to those constructed by thermodynamic criteria, only depending on πLL, which means that the novel boundary and Widom delta can extend to the supercritical deep region. Further, the visualization and radial distribution function of simulated systems of supercritical CO2 at different states provide the persistence of a liquid-like and a gas-like transition. The work conducted here can present novel microscopic insight into supercritical phase transition and provide another available alternative to define the Widom line.

Determining the Bimodal Soil–Water Characteristic Curve of Fine-Grained Subgrade Soil Derived from the Compaction Condition by Incorporating Pore Size Distribution

The soil–water characteristic curve (SWCC) is a key constitutive relationship for unsaturated soil which can be unimodal or bimodal. For the fine-grained compacted subgrade soil with a bimodal pattern, the determination of SWCC is complicated and needs a wide-range suction measurement. In this paper, the bimodal SWCC of a subgrade soil derived from the compaction condition was measured and determined by incorporating pore size distribution. For this purpose, a series of laboratory tests were conducted, including the pressure plate method, filter paper method, and vapor equilibrium method, which were used to measure SWCC at the low, medium, and high suction range, respectively. The pore size distribution (PSD) data were obtained by mercury intrusion porosimetry (MIP) tests and used to predict SWCC. Based on the analysis of hydraulic paths and SWCC-PSD correlations, the SWCC of the subgrade soil should be determined to follow the actual hydraulic path. SWCC within a low suction range can be filled by PSD-based data to improve the fitting accuracy. Then, a graphical method is applied to predict the bimodal SWCC by combining the filter paper method, vapor equilibrium method, and PSD-based data. The prediction curves fit well with the test data for all selected compaction conditions. Furthermore, the prediction method can still provide good prediction performance in the absence of high suction section data, which is beneficial for the application of bimodal SWCC.

Moisture Performance Requirements for Insulation in Exterior Wood-Frame Walls without a Vapour Barrier

An increased interest has been observed, especially among architects, in constructing the building envelope without using a vapour barrier membrane of polyethene (PE) foil. An increasing interest in biogenic building materials has also been expressed, as their use, besides storing embedded carbon, can reduce greenhouse gas emissions, replacing nonrenewable building components. Further, building envelope construction without a vapour barrier reduces expenses and the difficulty of the work process, especially around joints and penetrations. This study aims to determine the most important material properties of biogenic thermal insulation materials that influence the moisture-robustness of exterior wood-frame walls constructed without a vapour barrier. A literature study was performed to examine which material parameters have the most influence on the moisture conditions in an exterior wall without a vapour barrier. Hygrothermal simulations of lightweight exterior walls were performed to investigate the significance of variations in material properties (e.g., equilibrium moisture content and vapour diffusion resistance) and determine their necessary characteristics when used as thermal insulation material in an exterior wall without a vapour barrier in internal humidity class 3 (defined in EN ISO 13788). The moisture-robustness of the construction is assessed based on the risk of mould growth in the layer between the thermal insulation and wind barrier. The study suggests that the moisture capacity of the available common biogenic thermal insulation materials does not significantly affect the overall moisture performance of the wall. Simulations demonstrate that, for the thermal insulation layer in internal humidity class 3, at least one of the following requirements must be met to ensure moisture-robustness in exterior walls without a vapour barrier: (I) high diffusion resistance of the thermal insulation and (II) high moisture capacity of the thermal insulation material at relative humidity between 60% and 90%. Commercial biogenic thermal insulation materials on the market do not meet the latter requirement.

Effect of film thickness and temperature on condensation and momentum accommodation at the liquid–vapor methane interphase in contact with a quartz substrate

In this paper, we used the Molecular Dynamics method to simulate the equilibrium vapor–liquid methane in contact with a solid quartz substrate and study the condensation process and momentum exchange at the atomic level. A large potential cutoff radius is used to determine the vapor and liquid densities at good accuracy. By tracking the motions of fluid molecules exchanged between the vapor and liquid phases and carrying out statistical analysis of residence time, penetration depth and especially velocity correlation, the mass and the velocity accommodation coefficients can be determined at the same time. The latter is based on the assumption that the reflected events take place over a short time, near the interface and thus atoms velocities are correlated while the condensation/evaporation events are not. The calculated coefficients are sensitive to the film thickness due to the presence of the quartz substrate and the layering effects. As temperature increases, atoms condense less and reflect more and the reflection is more diffusive due to increasing collision rate. Near the critical temperature, both the condensation and momentum accommodation coefficients vary significantly.

Insights into tension‐mediated and antecedent water effects on soil water isotopic composition

AbstractUsing isotopic spike experiments, we investigated the existence and magnitude of soil‐mediated isotopic effects and of the interaction between isotopically distinct soil water pools, both associated in isotopic mismatches between water extracted from soil and soil water taken up by the roots. For this, we applied and compared four established techniques commonly used for the extraction of water (vapor) from soil, three of them relying on destructive soil sampling (cryogenic vacuum distillation, centrifugation, and direct water vapor equilibration), and one being a nondestructive in situ online technique. We observed an almost complete mixing of sequentially added, isotopically distinct water samples to a pure quartz sand (memory effect). The isotopic composition of water held at high soil tension in the pure quartz sand (pF = 2) as well as in a sandy soil (pF = 1.8 and 3) deviated considerably from that of the added water (tension effect). However, we could attribute this deviation not exclusively to a soil‐mediated effect but also to methodological shortcomings during our experiments. Finally, we found the following decreasing trend in precision as well as in accuracy of the used water extraction methods: in situ online > centrifugation > direct water vapor equilibration > cryogenic vacuum distillation. The investigation of isotopic fractionation of soil water due to physicochemical processes in soil can be facilitated if the experimental techniques used do not involve isotopic fractionation. In addition, methodological uncertainties and inaccuracies can be minimized by method standardization, increasing the potential of water stable isotopic monitoring in ecohydrological studies.

Soil total suction sensing using fiber-optic technology

Measurement of the soil water suction is important for investigating geotechnical problems and mitigating associated risks; however, conventional high-range suction measurement techniques have some limitations for accurate, long-term, and quasi-distributed suction measurement in the field. Fiber-optic humidity sensors provide a viable solution due to their unique properties. Here, we present a novel microfabricated fiber-optic suction sensor for measuring the suction of water in unsaturated soils. We evaluated the performance of the sensor on four bentonite–sand mixtures by comparing it with two laboratory suction measurement methods (chill-mirror hygrometer, salt solution vapor equilibrium) and a capacitive relative humidity sensor. We determined that this sensor has a measurement range of 5–300 MPa with a root mean square error of less than 3.5 MPa, and a response time of 2–9 min over the tested suction variation range (6.5–80.5 MPa). The results of the evaporation model test showed that three fiber-optic sensors installed at different depths of bentonite could effectively capture changes in temperature, relative humidity in soil pores, and total suction during evaporation. Together, these results demonstrate the great potential of the fiber-optic suction sensor for in-situ, long-term, and quasi-distributed suction monitoring.

Nucleation of a Vapor Phase and Vapor Front Dynamics Due to Boiling-Up on a Solid Surface

The effect of temperature and pressure on the nucleation of the vapor phase and the velocity of the vapor front in the initial stage of activated boiling-up of n-pentane on the surface of a quartz fiber was studied. Using a developed approach combining the “pump-probe” and laser Doppler velocimetry methods, this velocity was tracked in the course of sequential change in the degree of superheating with respect to the liquid–vapor equilibrium line. The studied interval according to the degree of superheating was 40–100 °C (at atmospheric pressure). In order to spatiotemporally localize the process, the activation of boiling-up at the end of the light guide was applied using a short nanosecond laser pulse. A spatial locality of measurements was achieved in units of micrometers, along with a time localization at the level of nanoseconds. An increase in temperature at a given pressure was found to lead to an increase in the speed of the transition process with a coefficient of about 0.2 m/s per degree, while an increase in pressure at a given temperature leads to a decrease in the transition process speed with a coefficient of 25.8 m/s per megapascal. The advancement of the vapor front velocity measurements to sub-microsecond intervals from the first signs of boiling-up did not confirm the existence of a Rayleigh expansion stage with a constant velocity.

An experimental study on the measurement of gas diffusivities in un-saturated clay based materials

Gas migration in porous media in the context of nuclear waste disposal is dominated by diffusion. The availability of abundant data on diffusion coefficients of different gases in many clay based materials such as Boom Clay, Opalinus Clay and Callovo-Oxfordian Clays provides a good overview of the rates of gas transport through these different clay rocks [1]. Such formations are being considered as potential host rocks for the disposal of high and intermediate level radioactive wastes across Europe. Diffusion coefficients have been studied with particular interest due to the unavoidable gas generation phase in the nuclear waste repository [2]. However, all the diffusion measurements performed so far have been under fully saturated conditions, with little experimental data on gas diffusivities in partially saturated conditions, which have been hypothesized to exist during the early part of the life cycle of the repository [3]. The objective of the current study is to provide an overview of the effect of desaturation on the rate of diffusive transport of gases in partially saturated clay based materials.
 The experimental methodology is based on the double through diffusion setup used in previous studies to measure gas diffusivities in saturated clays [1]. However, the setup is modified so as to keep a fixed level of unsaturation in the clay sample. This is done by employing the vapour equilibrium technique, using oversaturated salt solutions in both upstream and downstream reservoirs to maintain a constant relative humidity in the entire setup [4].
 Preliminary pore network modelling has already shown that the gas diffusivity increases with a decrease in water saturation of the clay material. However, the predicted trend also suggests that this increase is only marginal and should not normally exceed an order of magnitude. This is shown in the figure below.
 All the diffusion measurements are carried out on synthetic clay samples of dimensions 3.8 cm (diameter) and 2 cm (height). In Table 1, the Sw stands for water saturation. The compositions of the synthetic clay samples (60% clay, 20% sand, 20% silt) have been adjusted so as to most closely mimic the mineralogical compostion of Boom Clay. Synthetic samples are used instead of natural samples like Boom Clay because of their better physical response to drying than Boom Clay.
 The selected control variable to lower the saturation of the material is suction, which is imposed by changing the relative humidity of the environment using oversaturated salt solutions [4]. Suction can be kept constant given constant ambient temperature and pressure. Thus, the clay sample is conditioned at a certain suction, which in turn leads to desaturation in the range of 70-100% of total saturation depending on the level of suction. For this study, the saturation range has been fixed in between 70-100% of total saturation. This range has been chosen because of what is expected in a real life nuclear waste repository. The first measured diffusion coefficients in two partially saturated samples are shown in Table 1. The initial measurements of gas diffusion coefficients in unsaturated synthetic clays show that the increase in diffusivity of helium is higher than that of argon. Helium is the second lightest known element and has an extremely small molecular size and hence the impact of desaturation on helium diffusivity could be more pronounced than the same for heavier gases.

Microbial growth under drought is confined to distinct taxa and modified by potential future climate conditions

Climate change increases the frequency and intensity of drought events, affecting soil functions including carbon sequestration and nutrient cycling, which are driven by growing microorganisms. Yet we know little about microbial responses to drought due to methodological limitations. Here, we estimate microbial growth rates in montane grassland soils exposed to ambient conditions, drought, and potential future climate conditions (i.e., soils exposed to 6 years of elevated temperatures and elevated CO2 levels). For this purpose, we combined 18O-water vapor equilibration with quantitative stable isotope probing (termed ‘vapor-qSIP’) to measure taxon-specific microbial growth in dry soils. In our experiments, drought caused >90% of bacterial and archaeal taxa to stop dividing and reduced the growth rates of persisting ones. Under drought, growing taxa accounted for only 4% of the total community as compared to 35% in the controls. Drought-tolerant communities were dominated by specialized members of the Actinobacteriota, particularly the genus Streptomyces. Six years of pre-exposure to future climate conditions (3 °C warming and + 300 ppm atmospheric CO2) alleviated drought effects on microbial growth, through more drought-tolerant taxa across major phyla, accounting for 9% of the total community. Our results provide insights into the response of active microbes to drought today and in a future climate, and highlight the importance of studying drought in combination with future climate conditions to capture interactive effects and improve predictions of future soil-climate feedbacks.

Method for Obtaining Isothermal Diagrams of the Liquid - Vapor Equilibrium for the System as Dimethyl Zinc - Dimethyl Telluride

According to the obtained experimental temperature dependences of the saturated vapor pressure on dimethylzinc – dimethyltelluride solutions with dimethylzinc content of 50.0 and 70.32 mol. %, isothermal sections (280, 290, 300, 310, and 320 K) were made. For the dimethylzinc – dimethyltelluride system based on a limited set of experimental data for the “liquid-vapor” equilibrium, the vapor composition was calculated according to the Duhem – Margules equation, as well as the partial pressures and the distribution coefficient.

(Invited) Mechanism of H2 Synthesis Due to Plasma-Induced Water Splitting Via Free-Electron Impact

The electrified plasma-liquid interface (EPLI) has two major local reactors, the plasma phase and the liquid phase. Both local reactors enable water splitting, but their synthesis mechanism is different. While the mechanism of H2 synthesis in a liquid phase (plasma electrochemistry) was reasonably deciphered, the respective mechanism in the plasma phase does not (plasma chemistry). In this present contribution, the Chemical Reaction Network (CRN) analysis serves as a tool to decipher the H2 synthesis mechanism in the plasma reactor. For that, the datum from the laboratory of Sankaran serves as grounds for the CNR analysis. Sankaran team identified that the equilibrium vapor pressure of water introduces water vapor in the plasma phase; and that, fundamentally, there were eight elementary reactions involved in the plasma-chemistry mechanism of H2 synthesis, i.e., those reactions containing the largest constant rates (or electron rate coefficients). [1] The authors obtained the reaction rate constants via a numerical solution of the Boltzmann equation (BE) for electrons in weakly ionized gases considering the uniform electrical field. [2] Together, those eight elementary reactions form the following global reaction for the water splitting via electron-impact8 H2O → ●H+ ●OH + ●O + O– + O+ + OH– + OH+ + H– + H+ that is also rationalized in terms of global CRN, shown in figure 1. The water molecule splits into two major classes of fragments, the radical fragment set {●H, ●OH and ●O} and the ionic fragment set {O–, O+, OH–, OH+, H–, H+}. These two classes of fragments receive different treatments in this work because their kinetic relaxation is supposed to follow different time scales. The radical fragment is supposed to relax toward final products much faster than the ionic fragments. For this reason, only the chemical dynamics of the radical fragment are considered in the relaxation step toward the final products. The chemical dynamics of relaxation toward final products, thus, take into account only the set of radical fragments. This talk will present and discuss the chemical reaction network (CRN) for the relaxation of the radical fragment toward final products like hydrogen (H2), hydrogen peroxide (H2O2), water (H2O), and eventually oxygen (O2). The radical-relaxation CNR is not shown in this abstract but will be present/discussed in the talk.Roughly speaking, the radical-relaxation dynamics must deliver hydrogen as the major product and hydrogen peroxide as the major side-product, besides a stochiometric ratio of 4 to 1, respectively. Specifics on whether the radicals •OH relaxes toward H2O2 or H2O depend on the local dynamics, meaning that it mostly relies on the parameter set values that drive the CRN. Unfortunately, there is no experimental evidence already reporting the stoichiometry of products, which makes it unfeasible to evaluate the adherence of our analysis to the experimental pieces of evidence.

Moisture-driven CO2 pump for direct air capture

Direct Air Capture, the chemical separation of carbon dioxide (CO2) from air, is considered a necessary approach to generate negative carbon emissions and in turn limit global warming, though energetic and monetary costs must continue to decline to meet the needed gigaton scale. The promise of energy-efficient and continuous carbon dioxide membrane separation has only recently been investigated with the development of facilitated chemical transport and novel electrochemically driven methods. This work demonstrates the potential for continuous pumping of CO2 from air using commercial anion exchange membranes driven solely by a water vapor gradient. A reactive transport model that couples ionic transport with moisture sensitive bicarbonate chemistry in charged polymers, also termed moisture swing sorption, was developed alongside experimentally measured equilibrium and transport properties of CO2 and water vapor in Fumasep FAA-3 to determine the mass transport limits of such a system. The results show that the commercial membrane is kinetically limited by the moisture sensitive chemistry, enabling a CO2 current of 1.1 μmol/m2∙ s. In diffusion limited materials, a CO2 pumping flux can reach 11 μmol/m2∙ s in and peak performance is expected with a dry air relative humidity around 50% pumping into a saturated water vapor permeate. In all configurations, water loss becomes the major cost in such a separation and must be managed through optimal polymer design or water recovery mechanisms. The work demonstrates the applicability of a new driving force, the evaporation of water, to meet the energetic demand of CO2 separation from air.

Liquid–Vapor Equilibrium in a Toluene–Methanol–N-Octylquinolinium Bromide System

The liquid–vapor equilibrium in the toluene–methanol–N-octylquinolinium bromide system has been studied at 101.3 kPa and various concentrations of the organic salt. It was shown that the quinolinium salt can be used as a separating agent for a toluene–methanol azeotrope mixture. For breaking the azeotrope and separating the mixed solvent into components, the N-octylquinolinium bromide concentration (in mole fractions) should be 0.55 or higher.

Trace Ammonia Equilibrium Pressure of Zirconium Phosphate in Moisture.

Zirconium phosphate-absorbed ammonia gas and the ammonia concentration (pressure) decreased to 2 ppm (ca. 20 Pa). However, it has not been clarified what the equilibrium pressure of zirconium phosphate is during ammonia gas ab/desorption. In this study, the equilibrium pressure of zirconium phosphate during ammonia ab/desorption was measured using cavity ring-down spectroscopy (CRDS). For ammonia-absorbed zirconium phosphate, a two-step equilibrium plateau pressure was observed during the ammonia desorption in gas. The value of the higher equilibrium plateau pressure at the desorption process was about 25 mPa at room temperature. If the standard entropy change (ΔS0) of the desorption process is assumed to be equal to the standard molar entropy of ammonia gas (192.77 J/mol(NH3)/K), the standard enthalpy change (ΔH0) is about -95 kJ/mol(NH3). In addition, we observed hysteresis in zirconium phosphate at different equilibrium pressures during ammonia desorption and absorption. Finally, the CRDS system allows the ammonia equilibrium pressure of a material in the presence of water vapor equilibrium pressure, which cannot be measured by the Sievert-type method.