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At least 55 records · Page 3

Understanding and Mitigating Stickiness in Biochar Produced through Acid Hydrolysis and Dehydration

Levulinic acid is a platform chemical with significant potential for conversion into a wide range of biobased chemicals and fuels. A common process for producing levulinic acid from lignocellulosic feedstocks involves acid hydrolysis and dehydration (AHDH), where hexose polymers are hydrolyzed into monomeric sugars and subsequently dehydrated to levulinic acid and formic acid in the presence of dilute sulfuric acid. However, scaling the AHDH process is challenging because of the formation of byproducts such as sticky biochar, which accumulates in continuous-flow reactors, reducing effective reaction volume and increasing process downtime. This study investigates the effect of a chemical preconditioning step on mitigating sticky biochar formation. Woody biomass was preconditioned at 170 °C with 0.26 wt % sulfuric acid for 30 min, resulting in substantial removal of hemicellulose and acid-soluble lignin. AHDH of these preconditioned solids produced biochar that did not adhere to reactor surfaces. TGA analysis confirmed that the chemical preconditioning step minimized interactions between hemicellulose-derived degradation products and lignin side chains, reducing sticky char formation. Additionally, the study observed a 6% higher yield of organic acids from softwood species compared to hardwoods, with bark content shown to negatively impact yield. These findings suggest that targeted preconditioning of lignocellulosic biomass can enhance reactor operability and improve organic acid production efficiency in AHDH processes.

biopolymers↗

Dehydration of Methyl Lactate on Alkali Cation-Exchanged Faujasite: Effects of Metal Cation Identity and Water Pressure

Turnover rates for the catalytic dehydration of methyl lactate (ML) over ion-exchanged faujasite (FAU) catalysts depend on the identity of alkali metal cations (Na + , K + , Cs + ) and local solvation effects. Analysis of rate measurements and in situ infrared spectroscopy gives evidence that the reaction involves kinetically relevant dissociation of adsorbed methyl lactate upon alkali metal cations. This process involves concerted methyl transfer to the surface and dissociation of the alkali metal from the framework, which occurs at cationic active sites that remain predominantly unoccupied under relevant conditions (0.5–10 kPa ML, 0.5–15 kPa H 2 O, 563–583 K). Despite the mechanistic similarities, apparent activation enthalpies (ΔH app ‡ ) decrease linearly (47 kJ mol –1 from Na + to Cs + ) with ionization energy and cationic radius, and apparent activation entropies (ΔS app ‡ ) decrease 74 J mol –1 K –1 . These trends reflect electrostatic interactions that stabilize the cations to the anionic sites on the zeolite: stronger association between these charges leads to increasingly endothermic processes to displace the alkali metal to form a cationic methoxy and an intrapore metal lactate intermediate. Water physisorption measurements suggest alkali metal ions bind superstoichiometric quantities of water within FAU pores, and in situ infrared spectra suggest the concerted adsorption of ML requires reorganization of this water. Consequently, these processes introduce entropic gains that partially offset entropy losses associated with ML adsorption. Hence, turnover rates differ only by a factor of 2 among Na-, K-, and Cs-FAU at 573 K (ΔΔG app ‡ = 5 kJ mol –1 ). These findings demonstrate the interplay of alkali metal ions with zeolite active sites and intrapore water clusters for ML dehydration, indicating that these interactions can be leveraged to deliver optimal performance under different reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectral effects of dehydration on phyllosilicates

Six phyllosilicates were progressively dehydrated under controlled conditions in an effort to study the spectral effects of their dehydration. The spectra obtained at each level of hydration provide information that may be used in future spectroscopic observations of the planets, as well as a data set which compliments the existing body of terrestrial soil knowledge.

Bruckenthal, E. A.↗

Dehydration in the lower Antarctic stratosphere in late winter and spring

The history of minimum temperatures at 50 and 70 mb is examined from NMC, UK Met 0 and ECMWF analyses. MSU channel 24 data are similarly inspected. South Pole sonde data are used to calculate saturation humidity mixing ratio as a function of altitude and time throughout 1987. Saturation with respect to ice could be maintained for water mixing ratios of 3.5 ppmv for a period of about 80 days from mid-June to mid-September. Dehydration to mixing ratios of 1 ppmv or less was possible sporadically. Data from the ER-2 flights between 53 S and 72 S are used in conjunction with particle size measurements and air parcel trajectories to demonstrate the dehydration occurring over Antarctica. Water mixing ratios at the latitude of Punta Arenas (53 S), in conjunction with tracer measurements and trajectory analysis, show that at potential temperatures from about 325 to 400 K, the dryness (less than 3 ppmv) had its origin over Antarctica rather than in the tropics. Water mixing ratios within the Antarctic vortex varied from 1.5 to 3.8 ppmv, with a strong isentropic gradient being evident in the region of high potential vorticity gradients.

Kelly, K. K.↗

Dehydration in the lower Antarctic stratosphere during late winter and early spring, 1987

The history of minimum temperatures at 50 and 70 mb is examined from NMC, UK Met O and ECMWF analyses. MSU channel 24 data are similarly inspected. South Pole sonde data are used to calculate saturation humidity mixing ratio as a function of altitude and time throughout 1987. Saturation with respect to ice could be maintained for water mixing ratios of 3.5 ppmv for a period of about 80 days from mid-June to mid-September. Dehydration to mixing ratios of 1 ppmv or less was possible sporadically. Data from the ER-2 flights between 53 S and 72 S are used in conjunction with particle size measurements and air parcel trajectories to demonstrate the dehydration occurring over Antarctica. Water mixing ratios at the latitude of Punta Arens (53 S), in conjunction with tracer measurements and trajectory analysis, show that at potential temperatures from about 325 to 400 K, the dryness (less than 3 ppmv) had its origin over Antarctica rather than in the tropics. Water mixing ratios within the Antarctic vortex varied from 1.5 to 3.8 ppmv, with a strong isentropic gradient being evident in the region of high potential vorticity gradients.

Kelly, K. K.↗

The January 30, 1989 Arctic polar stratospheric clouds (PSC) event - Evidence for a mechanism of dehydration

In-situ particle measurements made aboard the NASA ER-2 in the Arctic on 890130 (YYMMDD) show Type 1 PSC particles over much of the flight, with instances of embedded Type 2 PSCs. The Type 2 particles were observed at temperatures warmer than the local frost-point temperature of water; extended up to the upper size cutoff of the instrument (about 24-micron diameter); and are shown to contain too large a volume to be primarily NAT. Based on measured vertical temperature profiles, it is concluded that the Type 2 particles observed on this day were formed above the aircraft in a region where saturation with respect to ice was achieved and were sufficiently large to have fallen into the path of the ER-2. Although the amount of material in the particles, expressed as water, is small by comparison to the total (vapor + aerosol) water concentration, the flux of water from the falling particles is of sufficient magnitude, if sustained, to lead to dehydration of the source region. These observations verify the mechanism for dehydration of polar vortex air masses by precipitation of ice particles.

Gandrud, B. W.↗

Radon measurements in the lower tropical stratosphere - Evidence for rapid vertical transport and dehydration of tropospheric air

During the tropical experiment of NASA's Stratosphere-Troposphere Exchange Program (STEP), in situ radon and other trace constituent measurements were made aboard a NASA ER-2 high-altitude research aircraft to investigate the mechanisms of irreversible transfers from the troposphere into the tropical stratosphere. Observations made in and downwind of the cirrus shields of three large tropical cyclones and downwind of the cirrus anvil of a large cumulonimbus cloud cluster showed several clear instances of elevated radon activity occurring simultaneously with low total water mixing ratios. These observations are unambiguous evidence of an effective dehydration process, capable of reducing total water vapor mixing ratios to less than 2.5 ppmv, occurring in conjunction with troposphere-to-stratosphere transport and indicate that rapid localized convection, rather than slow regional mean motions, was responsible for the observed transports and associated with the accompanying dehydration. Radon activities measured in regions of active or recent troposphere-to-stratosphere transport were consistent with the 17 pCi/scm mean value needed to support the observed abundance of stratospheric 210 Pb.

Kritz, Mark A.↗

Spring dehydration in the Antarctic stratospheric vortex observed by HALOE

The distribution of dehydrated air in the middle and lower stratosphere during the 1992 Southern Hemisphere spring is investigated using Halogen Occultation Experiment (HALOE) observations and trajectory techniques. Comparisons between previously published Version 9 and the improved Version 16 retrievals on the 700-K isentropic surface show very slight (0.05 ppmv) increases in Version 16 CH4 relative to Version 9 within the polar vortex. Version 16 H2O mixing ratios show a reduction of 0.5 ppmv relative to Version 9 within the polar night jet and a reduction of nearly 1.0 ppmv in middle latitudes when compared to Version 9. The version 16 HALOE retrievals show low mixing ratios of total hydrogen (2CH4 + H2O) within the polar vortex on both 700 and 425 K isentropic surfaces relative to typical middle-stratospheric 2CH4 + H2O mixing ratios. The low 2CH4 + H2O mixing ratios are associated with dehydration. Slight reductions in total hydrogen, relative to typical middle-stratospheric values, are found at these levels throughout the Southern Hemisphere during this period. Trajectory calculations show that middle-latitude air masses are composed of a mixture of air from within the polar night jet and air from middle latitudes. A strong kinematic barrier to large-scale exchange is found on the poleward flank of the polar night jet at 700 K. A much weaker kinematic barrier is found at 425 K. The impact of the finite tangent pathlength of the HALOE measurements is investigated using an idealized tracer distribution. This experiment suggests that HALOE should be able to resolve the kinematic barrier, if it exists.

Pierce, R. Bradley↗

CD4(+)/CD8(+) T-lymphocyte Ratio: Effects of Rehydration before Exercise in Dehydrated Men

Effects of fluid ingestion on CD4+/CD8+ T-lymphocyte cell ratios were measured in four dehydrated men (ages 30-46 yr) before and after 70 min of supine submaximal (71 % VO(sub 2max) lower extremity cycle exercise. Just before exercise, Evans blue dye was injected for measurement of plasma volume. The subjects then drank one of six fluid formulations (12 ml/kg) in 3-4 min. All six mean post-hydration (pre-exercise) CD4+/CD8+ ratios (Becton-Dickinson Fluorescence Activated Cell Sorter and FACScan Consort-30 software program were below the normal range of 1.2-1.5; mean (+/- SE) and range were 0.77 +/- 0.12 and 0.39-1.15, respectively. The post-exercise ratios increased: mean = 1.36 =/- 0.15 (P less than 0.05) and range = 0.98-1.98. Regression of mean CD4+/CD8+ ratios on mean plasma osmolality resulted in pre- and post-exercise correlation coefficients of -0.76 (P less than 0.10) and -0.92 (P less than 0.01), respectively. The decreased pre-exercise ratios (after drinking) were probably not caused by the Evans blue dye but appeared to be associated more with the stress (osmotic) of dehydration. The increased post-exercise ratios to normal levels accompanied the rehydration and were not due to the varied electrolyte and osmotic concentrations of the ingested fluids or to the varied vascular volume shifts during exercise. Thus, the level of subject hydration and plasma osmotality may be factors involved in the mechanism of immune system modulation induced by exercise.

Greenleaf, John E.↗

Experimental dehydration of natural obsidian and estimation of DH2O at low water contents

Water diffusion experiments were carried out by dehydrating rhyolitic obsidian from Valles Caldera (New Mexico, USA) at 510-980 degrees C. The starting glass wafers contained approximately 0.114 wt% total water, lower than any glasses previously investigated for water diffusion. Weight loss due to dehydration was measured as a function of experiment duration, which permits determination of mean bulk water diffusivity, mean Dw. These diffusivities are in the range of 2.6 to 18 X 10(-14) m2/s and can be fit with the following Arrhenius equation: ln mean Dw (m2/s) = -(25.10 +/- 1.29) - (46,480 +/- 11,400) (J/mol) / RT, except for two replicate runs at 510 degrees C which give mean Dw values much lower than that defined by the above equation. When interpreted according to a model of water speciation in which molecular H2O is the diffusing species with concentration-independent diffusivity while OH units do not contribute to the transport but react to provide H2O, the data (except for the 510 degrees C data) are in agreement with extrapolation from previous results and hence extend the previous data base and provide a test of the applicability of the model to very low water contents. Mean bulk water diffusivities are about two orders of magnitude less than molecular H2O diffusivities because the fraction of molecular H2O out of total water is very small at 0.114 wt% total water and less. The 510 degrees C experimental results can be interpreted as due to slow kinetics of OH to H2O interconversion at low temperatures.

NASA Program Exobiology↗

Bonding by Hydroxide-Catalyzed Hydration and Dehydration

A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.

Gwo, Dz-Hung↗

Electrolyte Concentrates Treat Dehydration

Wellness Brands Inc. of Boulder, Colorado, exclusively licensed a unique electrolyte concentrate formula developed by Ames Research Center to treat and prevent dehydration in astronauts returning to Earth. Marketed as The Right Stuff, the company's NASA-derived formula is an ideal measure for athletes looking to combat dehydration and boost performance. Wellness Brands also plans to expand with products that make use of the formula's effective hydration properties to help treat conditions including heat stroke, altitude sickness, jet lag, and disease.

Source record↗

Facet-Dependent Water Inhibition of Alkanol Dehydration on TiO2 via Distinct Water–Alkanol Complexes

Water is ubiquitous in biomass-derived feeds, yet its molecular impact on oxygen-elimination reactions remains poorly understood, particularly for catalysts exposing different facets. Here, we utilize well-defined TiO2 nanocrystals with dominant (101) and (001) facets to reveal a pronounced facet-dependent effect of water, where inhibition for dehydration of isopropanol (IPA) on the TiO2(001) surface is about four times more severe than TiO2(101). Through a combination of in situ solid state NMR, in situ infrared spectroscopy, kinetics studies, and theoretical calculations, we demonstrate that this disparity arises from the formation of distinct alkanol-water complex intermediates. On TiO2(001), IPA undergoes dissociative adsorption to form an isopropoxide-H2O complex that readily drives the surface into a complex-dominated regime. This pathway increases the activation barrier for C–H cleavage by 40 kJ mol-1 by inducing a disordered transition state. In contrast, TiO2(101) favors molecular IPA adsorption with weak hydrogen bonding to water, resulting in a smaller complex formation constant and a much smaller activation barrier increase (25 kJ mol-1). By quantitatively linking facet-dependent complex coverage to transition-state destabilization, this work moves beyond simple site-blocking models and provides a conceptual framework for designing catalysts that remain active in water-containing environments

Hu, Wenda↗