Equilibrium Water Vapor Pressure Research Articles

(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.

Cloud Droplet Nucleation Simulation and Parameterization

Abstract Cloud droplet nucleation is classically defined as a droplet growing to a size such that its ambient supersaturation exceeds its surface equilibrium water vapor pressure. Unactivated particles are always in equilibrium with the ambient vapor pressure. Further studies showed that such an equilibrium assumption leads to many more cloud droplets being nucleated due to neglecting kinetic growth limitations, including the inertial mechanism, evaporation mechanism, and deactivation mechanism. Moreover, the inertial mechanism results in great discrepancy between the actual size and the critical size of nucleation for large aerosol particles. These issues complicate cloud droplet nucleation parameterization for applications in cloud modeling. To establish a physically based nucleation scheme, we established a highly size-resolved Lagrangian parcel model. Vapor diffusion and heat conduction were calculated according to Maxwell theory, and the surface vapor density and temperature were explicitly simulated. The surface temperature variation of a droplet with its size was considered. The surface supersaturation of a droplet, taking into account the surface temperature variation, is different from its equilibrium supersaturation at its large sizes. The nucleation simulation showed that the inertial and deactivation mechanisms can impact droplet nucleation. Moreover, very large nuclei can trigger rain embryo formation in a short time period. Even though there are kinetic limitations, the classical equilibrium assumption can be applied to determine the primary nucleation number of cloud droplets. Meanwhile, a regression formula for the size of a nucleated droplet and its dry aerosol size was established.

Dicationic-Type Quaternary Ammonium Salts as Candidates of Desiccants for an Air-Conditioning System

Liquid desiccant air conditioners contribute to sustainable living by reducing the electricity consumption. They can be driven with continuous ventilation and thus can prevent airborne transmission of infectious diseases like COVID-19. In order to develop efficient desiccant materials for liquid desiccant air conditioners, we have investigated the dehumidification capability of 21 types of ammonium salts, many of them being ionic liquids. The hygroscopicity of dicationic quaternary ammonium bis(dimethyl or diethylphosphate) is found to increase with the carbon chain length of the spacer group -(CH2)n- that bridges the two terminal cationic moieties of the dication, that is, (CH2)2 < (CH2)3 < (CH2)6. This trend remains unchanged when methyl substituents on the cation and the phosphate anion are replaced by ethyl groups. A high dehumidification capability is obtained for N1,N1,N1,N6,N6,N6-hexamethylhexane-1,6-diaminium bis(dimethylphosphate) ([HMC6][DMPO4]2) and 1,6-diethyl-1,1,6,6-tetramethylhexane-1,6-diaminium bis(diethylphosphate) ([DETMC6][DEPO4]2);their capability per gram reaches almost twice that of CaCl2, and their dehumidification rate is superior to popular solid desiccants. A favorable equilibrium water vapor pressure for the liquid desiccant air-conditioning system is attained for an 80% (w/w) aqueous solution of [HMC6][DMPO4]2. In addition, the 80% aqueous solution of [HMC6][DMPO4]2 affords no corrosive effect on steel, aluminum, and stainless steel and a very weak effect on copper. Dicationic quaternary ammonium bis(dimethyl or diethylphosphate)s are stable compounds;their aqueous solutions produce no odor after storing for over 1 year under ambient conditions. Molecular dynamics simulations are performed to gain insights into the solvation structure, energetics, and transport behavior of water in aqueous solutions of [HMC6][DMPO4]2 and related salts. ©

Structuring of reference data on the hygroscopic points of soluble substances

The article considers a way to expand the capabilities of the dynamic method for measuring hygroscopic points (equilibrium water vapour pressure over saturated solutions of substances) of solubles by applying it to an ordered series of substances with their hygroscopic points in a narrow range of (68–76)% RH. The experimentally measured values ​​of hygroscopic points are proposed as reference data on the hygroscopicity of such substances as carbamide, rubidium chloride, sodium nitrate, strontium chloride; the values for barium bromide and lithium perchlorate are clarified. The capability of the dynamic method to measure the difference between the hygroscopic points of substances enhances its consistency and reliability, makes it possible to present reference data in a structured form. Along with the simplicity of the procedure and the laboratory equipment used, this makes the proposed version of the dynamic method highly competitive among the other methods for determining water vapour pressure over saturated solutions of substances.

Discussion on Water Condensation in Membrane Pores during CO2 Absorption at High Temperature.

Water condensation is a possible cause of membrane wetting in the operation of membrane contactors, especially under high-temperature conditions. In this study, water condensation in pores of polytetrafluoroethylene (PTFE) hollow fiber membranes was investigated during high-pressure CO2 absorption around 70 °C. It was found that the liquid accumulation rate in the treated gas knock-out drum was constant during continuous operation for 24 h when all experimental conditions were fixed, indicating a stable degree of membrane wetting. However, as the operating parameters were changed, the equilibrium vapor pressure of water within membrane pores could change, which may result in a condensation-conducive environment. Water condensation in membrane pores was detected and proven indirectly through the increase in liquid accumulation rate in the treated gas knock-out drum. The Hagen–Poiseuille equation was used to correlate the liquid accumulation rate with the degree of membrane wetting. The degree of membrane wetting increased significantly from 1.8 × 10−15 m3 to 3.9 × 10−15 m3 when the feed gas flow rate was reduced from 1.45 kg/h to 0.40 kg/h in this study due to water condensation in membrane pores. The results of this study provide insights into potential operational limitations of membrane contactor for CO2 absorption under high-temperature conditions.

Design of quaternary ammonium type-ionic liquids as desiccants for an air-conditioning system

The liquid desiccant air-conditioning system allows reducing energy consumption compared to the conventional compressor-type air conditioners. In order to develop desiccant materials for air conditioners, we have investigated the dehumidification capability of quaternary ammonium Ionic Liquids (ILs) and the equilibrium water vapor pressure of aqueous solutions of these ammonium salts. Among the seven tested types of ILs, 2-hydroxy-N,N,N-trimethylethan-1-aminium dimethylphosphate ([Ch][DMPO4]) displayed the best dehumidification capability and the lowest equilibrium water vapor pressure. Furthermore, the 80% aqueous solution of [Ch][DMPO4] exhibited a less corrosive effect on four types of metals, i.e., steel (hot dip zinc-aluminum alloy plated steel), copper (C1100P), aluminum (A5052), and stainless steel (SUS: SUS304). It should be noted that this [Ch][DMPO4] is not only non-toxic but also exhibits a stable nature; the aqueous solution produced no odor after storing for over 1 year under ambient conditions.

Membrane condenser heat exchanger for conditioning of humid gases

Here we propose combined process for gas streams dehumidification using porous polypropylene membrane contactor heat-exchanger with liquid coolant absorbent and report the results on its operation performance. The technique enables effective removal of condensable components of gas mixtures to ultimate residual pressures by a synergetic contribution of two effects – suppression of the equilibrium water vapor pressure at low temperatures and water vapor removal by hygroscopic absorbent. The method is examined in the process of air stream dehumidification with ethylene glycol-water absorbents. Experimental data on the process performance at different gas fluxes (0.3–12 m3(STP)·m−2·h−1), pressures (2.5 – 9 bar), chilled absorbent temperatures (−30 ÷ 3 °C) and absorbent compositions (0–100 wt% of ethylene glycol) is reported. It is revealed the performance of contactor is mostly limited by viscosity of the cooling absorbent, allowing to achieve dew point temperature of the processed gas down to −30 °C with a water vapors stage cut over 90% at gas flux over 10 m3(STP)·m−2·h−1 and packing density of hollow fiber membrane up to 3000 m2/m3 with 35%:65% (wt.) water-ethylene-glycol absorbent. A technical scheme for industrial dehumidification setup is proposed and the results of the model setup performance are evaluated in comparison with traditional desiccant, wheel adsorbent and refrigeration processes. It is shown the proposed technique provides much wider range of acceptable gas dew point temperatures as compared to conventional refrigerant process and more preferred energetically compared to desiccant and wheel dehumidification.

Accurate vapor pressure measurements of supercooled water in the temperature range between 252 K and 273 K

The accurate knowledge of the saturation vapor pressure of liquid water and ice has a great importance in a host of applications where humidity measurements are involved since it enables the correct conversion among different physical quantities that quantify the water vapor amount of a humid gas mixture.More specifically, accurate saturation vapor pressure measurements of supercooled water are strongly required in meteorology and atmospheric sciences, especially in cloud microphysics studies.Considering the importance of this kind of measurements and the limited availability of experimental data in the literature, further measurements in the metastable region were carried out at the Istituto Nazionale di Ricerca Metrologica (INRIM).The sample cell used in the experiment is a U-shaped capillary tube made of borosilicate glass, whose temperature is kept constant by immersion in a thermostatic bath with a high temperature stability (about 1 mK). The cell is connected to a capacitive diaphragm pressure gauge measuring the equilibrium water vapor pressure, that varies between about 116 Pa at T = 252.25 K and 615 Pa at T = 273.25 K.In the present work, the measuring method and the experimental setup are described and the measurements results reported. The results obtained in the whole temperature range are compared with those available in the literature and with the commonly adopted saturation vapor pressure formulations. A complete uncertainty budget is also given, resulting in an expanded relative uncertainty ranging from 0.06% at 273.25 K to 0.20% at 252.25 K.

Molecular dynamics simulation of the surface tension of aqueous sodium chloride: from dilute to highly supersaturated solutions and molten salt

Abstract. Sodium chloride (NaCl) is one of the key components of atmospheric aerosols. The surface tension of aqueous NaCl solution (σNaCl,sol) and its concentration dependence are essential to determine the equilibrium water vapor pressure of aqueous NaCl droplets. Supersaturated NaCl solution droplets are observed in laboratory experiments and under atmospheric conditions, but the experimental data for σNaCl,sol are mostly limited up to subsaturated solutions. In this study, the surface tension of aqueous NaCl is investigated by molecular dynamics (MD) simulations and the pressure tensor method from dilute to highly supersaturated solutions. We show that the linear approximation of concentration dependence of σNaCl,sol at molality scale can be extended to the supersaturated NaCl solution until a molality of ∼10.7 mol kg−1 (i.e., solute mass fraction (xNaCl) of ∼0.39). Energetic analyses show that this monotonic increase in surface tension is driven by the increase in excess surface enthalpy (ΔH) as the solution becomes concentrated. After that, the simulated σNaCl,sol remains almost unchanged until xNaCl of ∼0.47 (near the concentration upon efflorescence). The existence of the “inflection point” at xNaCl of ∼0.39 and the stable surface tension of xNaCl between ∼0.39 and ∼0.47 can be attributed to the nearly unchanged excess surface entropy term (T⋅ΔS) and the excess surface enthalpy term (ΔH). After a “second inflection point” at xNaCl of ∼0.47, the simulated σNaCl,sol gradually regains the growing momentum with a tendency to approach the surface tension of molten NaCl (∼175.58 mN m−1 at 298.15 K, MD simulation-based extrapolation). This fast increase in σNaCl,sol at xNaCl&gt;0.47 is a process driven by excess surface enthalpy and excess surface entropy. Our results reveal different regimes of concentration dependence of the surface tension of aqueous NaCl at 298.15 K: a water-dominated regime (xNaCl from 0 to ∼0.39), a transition regime (xNaCl from ∼0.39 to ∼0.47) and a molten NaCl-dominated regime (xNaCl from ∼0.47 to 1).

Raoult's law revisited: accurately predicting equilibrium relative humidity points for humidity control experiments.

The humidity surrounding a sample is an important variable in scientific experiments. Biological samples in particular require not just a humid atmosphere but often a relative humidity (RH) that is in equilibrium with a stabilizing solution required to maintain the sample in the same state during measurements. The controlled dehydration of macromolecular crystals can lead to significant increases in crystal order, leading to higher diffraction quality. Devices that can accurately control the humidity surrounding crystals while monitoring diffraction have led to this technique being increasingly adopted, as the experiments become easier and more reproducible. Matching the RH to the mother liquor is the first step in allowing the stable mounting of a crystal. In previous work [Wheeler, Russi, Bowler & Bowler (2012). Acta Cryst. F68, 111-114], the equilibrium RHs were measured for a range of concentrations of the most commonly used precipitants in macromolecular crystallography and it was shown how these related to Raoult's law for the equilibrium vapour pressure of water above a solution. However, a discrepancy between the measured values and those predicted by theory could not be explained. Here, a more precise humidity control device has been used to determine equilibrium RH points. The new results are in agreement with Raoult's law. A simple argument in statistical mechanics is also presented, demonstrating that the equilibrium vapour pressure of a solvent is proportional to its mole fraction in an ideal solution: Raoult's law. The same argument can be extended to the case where the solvent and solute molecules are of different sizes, as is the case with polymers. The results provide a framework for the correct maintenance of the RH surrounding a sample.

Effect of Leaf Water Potential on Internal Humidity and CO2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure.

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flat surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO2, thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Our results indicate that the reduction in vapor pressures of water and CO2 could enhance plant water use efficiency up to about 10% at a leaf water potential of −2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. The omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups.

Influence of Corrosion Product on Corrosion Behavior of Carbon Steel in Atmospheric Environment

Atmospheric corrosion proceeds under thin water film, and it is affected by many environmental factors such as temperature, relative humidity, rainfall, deposition of airborne sea salt. Most of the previous study of atmospheric corrosion of carbon steel has been focused on the corrosion behavior in initial corrosion process. However, corrosion products are formed on the surface at an early stage in case of carbon steels. Thus it is important to clarify the influence of corrosion products on atmospheric corrosion behavior.. While corrosion products may easily lead to wet condition with absorption of moisture, it is reported that corrosion products inhibit the corrosion physically or chemically. In this study, we focus on dew condensation which occurs on the surface of carbon steels with rust layer. The electrodes with corrosion products were prepared by wet/dry cyclic corrosion test. The remodeled concentric corrosion sensor was used as the electrodes. The temperature of electrode materials can be controlled from the backside of electrode because the backside of the remodeled sensor is exposed to atmosphere. The corrosion test was carried out in a chamber at 25℃ and 60％RH by adding the droplet of 0.1M NaCl solution or distilled water. During the corrosion test, the corrosion rate of the electrode was monitored by electrochemical impedance method. The electrode covered with corrosion products was cooled with a cooling equipment in the chamber at 25 ℃ and 60 ％ RH in order to measure the dew point. The dew point was evaluated by measuring solution resistance using electrochemical impedance method. The dew point of the electrode before corrosion test was measured. The solution resistance dropped sharply to a low value at around 17 ℃. The dew point was calculated at 17℃ under the 25℃ and 60％RH from the curve of saturation water vapor pressure and Tetens’s equation, indicating that the experimental and calculated values are in good agreement. The amount of corrosion products increased with an increase of the cycle number. The solution resistance of the electrode after corrosion test went down at the temperature higher than the calculated value. In addition, the deposition of corrosion products occurred an increase of the dew point of the electrode. This is attributed to the diameter of pore in rust layer. It is known that equilibrium water vapor pressure in the crevice increases with a decrease of the crevice size. This means that the humidity in crevice increases in comparison with relative humidity of atmosphere. It is predicted the deposition of corrosion products leads to the formation of smaller size of pores. The chloride ion is included in the rust layer, and thus the water absorption of chloride ion occurs even at higher surface temperature.

Measuring and modeling the hygroscopic growth of two humic substances in mixed aerosol particles of atmospheric relevance

Abstract. The hygroscopic growth of atmospheric particles affects atmospheric chemistry and Earth's climate. Water-soluble organic carbon (WSOC) constitutes a significant fraction of the dry submicron mass of atmospheric aerosols, thus affecting their water uptake properties. Although the WSOC fraction is comprised of many compounds, a set of model substances can be used to describe its behavior. For this study, mixtures of Nordic aquatic fulvic acid reference (NAFA) and Fluka humic acid (HA), with various combinations of inorganic salts (sodium chloride and ammonium sulfate) and other representative organic compounds (levoglucosan and succinic acid), were studied. We measured the equilibrium water vapor pressure over bulk solutions of these mixtures as a function of temperature and solute concentration. New water activity (aw) parameterizations and hygroscopic growth curves at 25 °C were calculated from these data for particles of equivalent composition. We examined the effect of temperature on the water activity and found a maximum variation of 9% in the 0–30 °C range, and 2% in the 20–30 °C range. Five two-component mixtures were studied to understand the effect of adding a humic substance (HS), such as NAFA and HA, to an inorganic salt or a saccharide. The deliquescence point at 25 °C for HS-inorganic mixtures did not change significantly from that of the pure inorganic species. However, the hygroscopic growth of HA / inorganic mixtures was lower than that exhibited by the pure salt, in proportion to the added mass of HA. The addition of NAFA to a highly soluble solute (ammonium sulfate, sodium chloride or levoglucosan) in water had the same effect as the addition of HA to the inorganic species for most of the water activity range studied. Yet, the water uptake of these NAFA mixtures transitioned to match the growth of the pure salt or saccharide at high aw values. The remaining four mixtures were based on chemical composition data for different aerosol types. As expected, the two solutions representing organic aerosols (40% HS/40% succinic acid/20% levoglucosan) showed lower water uptake than the two solutions representing biomass burning aerosols (25% HS/27% succinic acid/18% levoglucosan/30% ammonium sulfate). However, interactions in multicomponent solutions may be responsible for the large variation of the relative water uptake of identical mixtures containing different HSs above a water activity of 0.95. The ZSR (Zdanovskii, Stokes, and Robinson) model was able to predict reasonably well the hygroscopic growth of all the mixtures below aw = 0.95, but produced large deviations for some multicomponent mixtures at higher values.

Measurement of the equilibrium relative humidity for common precipitant concentrations: facilitating controlled dehydration experiments.

The dehydration of crystals of macromolecules has long been known to have the potential to increase their diffraction quality. A number of methods exist to change the relative humidity that surrounds crystals, but for reproducible results, with complete characterization of the changes induced, a precise humidity-control device coupled with an X-ray source is required. The first step in these experiments is to define the relative humidity in equilibrium with the mother liquor of the system under study; this can often be quite time-consuming. In order to reduce the time spent on this stage of the experiment, the equilibrium relative humidity for a range of concentrations of the most commonly used precipitants has been measured. The relationship between the precipitant solution and equilibrium relative humidity is explained by Raoult's law for the equilibrium vapour pressure of water above a solution. The results also have implications for the choice of cryoprotectant and solutions used to dehydrate crystals. For the most commonly used precipitants (10-30% PEG 2000-8000), the starting point will be a relative humidity of 99.5%.

Hygroscopic growth of common organic aerosol solutes, including humic substances, as derived from water activity measurements

[1] Studies have shown that organic matter often constitutes up to 50% by mass of tropospheric aerosols. These organics may considerably affect the water uptake properties of these aerosols, impacting Earth's climate and atmosphere. However, considerable uncertainties still exist about hygroscopic properties of organic carbon (OC) in particles. In this study, we have assembled an apparatus to measure equilibrium water vapor pressure over bulk solutions. We used these results to calculate the hygroscopic growth curve and deliquescence relative humidity (DRH) of representative compounds in three OC categories: saccharides, mono/dicarboxylic acids, and HULIS (Humic-Like Substances). To our knowledge, this is the first study to examine the hygroscopic growth of HULIS by means of a bulk method on representative compounds such as fulvic and humic acids. We also explored the temperature effect on hygroscopic growth within the 0°C–30°C temperature range and found no effect. The DRH and hygroscopic growth obtained were in excellent agreement with published tandem differential mobility analyzer (TDMA), electrodynamic balance, and bulk data for sodium chloride, ammonium sulfate, d-glucose, levoglucosan, succinic acid, and glutaric acid. However, we found a hygroscopic growth factor of 1.0 at a relative humidity of 90% for phthalic, oxalic, humic, and two fulvic acids; these results disagree with various TDMA studies. The TDMA is used widely to study water uptake of organic particles but can be affected by particle microstructural arrangements before the DRH and by the inability to fully dry particles. Thus, in the future it will be important to confirm TDMA data for nondeliquescent organic particles with alternate methods.

Ca(OH)2 Superheating as a Low-Attrition Steam Reactivation Method for CaO in Calcium Looping Applications

Steam hydration of lime is an effective method for restoring CO2 capture activity but gives rise to high particle attrition rates in a fluid bed reactor. This paper describes the phenomenon of Ca(OH)2 superheating, also referred to as superheated dehydration (SD). The potential of an attrition-free lime reactivation process using this phenomenon is also investigated. Attrition rates of the sorbent are measured when a reactivation step using steam hydration is implemented every three carbonation/calcination cycles. It has been shown that the presence of CO2 during the dehydration step reduces attrition during subsequent cycles. Experiments performed in a small fluid bed reactor show that the presence of 40−100% CO2 during the dehydration step increases the initiation temperature of the decomposition of Ca(OH)2 from 445 to 618 °C. The thermodynamic equilibrium water vapor pressure for the dehydration reaction at 618 °C is 516 kPa, whereas no water vapor was detected in the reactor during the dehydration ste...

Une méthode mécanique pour mesurer la pression de vapeur d'équilibre de l'eau dans un milieu complexe

This Note presents a new method to measure the equilibrium vapour pressure of water in a complex medium. In this article a “complex medium” refers to a medium in which physico-chemical interactions alter the thermodynamical properties of the water, especially its activity and its equilibrium vapour pressure. This new method consists in placing a sample of the complex medium in a temperature-controlled chamber which volume can be incrementally increased by means of a piston. The equilibrium vapour pressure can be deduced from the variation of the equilibrium total pressure measured for each volume increment. The method has been validated on various saturated salt solutions and on a reference soil.

Thermal stability and thermodynamics of manganese(II) chloride monohydrate

Three tensimetric methods were used to measure the equilibrium water vapour pressure for the reaction MnCl 2 · H 2O(s) = MnCl 2(s) + H 2O(g) over the temperature range (353.25 to 500.3) K. Two additional effects were considered, viz. possibility of a hydrate super disperse phase formation and probability of manganese(II) chloride hydrolysis with water vapour. A linear equation was derived for the temperature dependence of the water vapour pressure: ln ( p / p ∘ ) = 14.981 - 7517 · ( K / T ) . The standard enthalpy and entropy of this process were calculated at the mean temperature 425 K: Δ r H ∘ (425) = (62,500 ± 200) J, Δ r S ∘ (425) = (124.56 ± 0.47) J · K −1. At the standard temperature these quantities were calculated using the approximate constant value of Δ r C P ∘ = ( - 8.3 ± 2 ) J · K - 1 · mol - 1 : Δ r H ∘ (298) = (63,550 ± 500) J, Δ r S (298) = (127.5 ± 1.2) J · K −1. Standard thermodynamic characteristics of manganese(II) chloride monohydrate were obtained: Δ f H m ∘ ( 298 ) MnCl 2 · H 2 O ( s ) = ( - 786.6 ± 0.9 ) kJ · mol - 1 ; S m ∘ ( 298 ) MnCl 2 · H 2 O ( s ) = ( 179.5 ± 1.6 ) J · K - 1 · mol - 1 .

Effects of Substrate Cooling during Sputter Deposition of Hydrogen-Containing Ta2O5 Thin Films in H2O Atmosphere on their Ion Conductivity

Hydrogen-containing Ta2O5 (Ta2O5:H) thin films, which are considered to be candidates for proton-conducting solid electrolytes, were prepared by reactive sputtering in H2O atmosphere. The substrate temperature during sputter deposition was changed from -20 to 70 °C because the equilibrium vapor pressure of water depends strongly on temperature. The chemical composition of the films was characterized by Rutherford backscattering (RBS) and hydrogen forward scattering (HFS), and it was found that the H/Ta atomic ratio increased with decreasing substrate temperature, and a maximum ratio of 2.2 was obtained at -20 °C. The ion conductivity measured at room temperature also increased with decreasing substrate temperature and a maximum conductivity of 4 ×10-8 S/cm was obtained at -20 °C. It is considered that the desorption rate of H2O molecules from the growing film surface was decreased by the substrate cooling, which resulted in the increase in the hydrogen content and the improvement of the ion conductivity.

Thermal stability and thermodynamics of copper(II) chloride dihydrate

Four tensimetric methods were used to measure the equilibrium water vapour pressure for the reaction 1/2CuCl2 · 2H2O(s) = 1/2CuCl2(s) + H2O(g) in the temperature range (301.40 to 404.65) K. Formation of the metastable hydrate super disperse phase [O.G. Polyachenok, E.N. Dudkina, N.V. Branovitskaya, L.D. Polyachenok, Thermochim. Acta 467 (2008) 44–53] was taken into account at studying this process. A linear equation was derived for the temperature dependence of the water vapour pressure: ln(p/p∘) = 17.237 − 6980.4 · (K/T). Standard enthalpy and entropy of this process were calculated at the mean temperature 358 K: ΔrH∘(358) = 58038 ± 73 J, ΔrS∘(358) = 143.32 ± 0.21 J · K−1. These data being processed together with the results of [R. Perret, Bull. Soc. Chim. France 2 (1966) 755–758] enabled to obtain the change of heat capacity ΔrCp∘=-10±2J·K-1·mol-1, and hence a more precise trinomial equation was deduced: ln(p/p°) = 25.515 – 7409.4 · (K/T) – 1.203 · ln(T/K). Standard thermodynamic characteristics of copper(II) chloride and its dihydrate were obtained: ΔfHm∘(298)CuCl2(s)=-219.1±1.8kJ·mol-1; Sm∘(298)CuCl2·2H2O(s)=195.3±1.4J·K-1·mol-1; Cp,m∘(298)CuCl2·2H2O(s)=159±4J·K-1·mol-1.