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At least 235 records · Page 13

Degradation of Adsorbed Bisphenol A by Soluble Mn(III)

Bisphenol A (BPA), a high production volume chemical and potential endocrine disruptor, is found to be associated with sediments and soils due to its hydrophobicity (log K OW of 3.42). Here, we used superfine powdered activated carbon (SPAC) with a particle size of 1.38 ± 0.03 μm as a BPA sorbent and assessed degradation of BPA by oxidized manganese (Mn) species. SPAC strongly sorbed BPA, and desorption required organic solvents. No degradation of adsorbed BPA (278.7 ± 0.6 mg BPA g –1 SPAC) was observed with synthetic, solid α-MnO 2 with a particle size of 15.41 ± 1.35 μm; however, 89% mass reduction occurred following the addition of 0.5 mM soluble Mn(III). Small-angle neutron scattering data suggested that both adsorption and degradation of BPA occurred in SPAC pores. The findings demonstrate that Mn(III) mediates oxidative transformation of dissolved and adsorbed BPA, the latter observation challenging the paradigm that contaminant desorption and diffusion out of pore structures are required steps for degradation. Soluble Mn(III) is abundant near oxic-anoxic interfaces, and the observation that adsorbed BPA is susceptible to degradation has implications for predicting, and possibly managing, the fate and longevity of BPA in environmental systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidative Catalytic Fractionation of Lignocellulosic Biomass under Non-alkaline Conditions

Biomass pretreatment methods are commonly used to isolate carbohydrates from biomass, but they often lead to modification, degradation, and/or low yields of lignin. Catalytic fractionation approaches provide a possible solution to these challenges by separating the polymeric sugar and lignin fractions in the presence of a catalyst that promotes cleavage of the lignin into aromatic monomers. In this work, we demonstrate an oxidative fractionation method conducted in the presence of a heterogeneous non-precious-metal Co-N-C catalyst and O 2 in acetone as the solvent. The process affords a 15 wt% yield of phenolic products bearing aldehydes (vanillin, syringaldehyde) and carboxylic acids (p-hydroxybenzoic acid, vanillic acid, syringic acid), complementing the alkylated phenols obtained from existing reductive catalytic fractionation methods. The oxygenated aromatics derived from this process have appealing features for use in polymer synthesis and/or biological funneling to value-added products, and the non-alkaline conditions associated with this process support preservation of the cellulose, which remains insoluble at reaction conditions and is recovered as a solid.

09 BIOMASS FUELS↗

Radiolytic evaluation of acetohydroxamic acid (AHA) under biphasic (n-dodecane and TBP/DEHBA/DEHiBA) used nuclear fuel reprocessing conditions

Acetohydroxamic acid (AHA) has been proposed as a substitute for uranium(IV) and hydrazine as a plutonium complexant and neptunium reductant for simplified, single-cycle used nuclear fuel reprocessing flowsheets. However, the chemical behavior of AHA in an intense multi-component radiation field is poorly understood, especially under representative biphasic reprocessing solvent system conditions. In response to this critical knowledge gap, this study has investigated the gamma radiolytic integrity of AHA in aqueous nitric solutions in contact with an organic phase, comprising current and future reprocessing ligands (TBP, DEHBA, and DEHiBA) dissolved in n-dodecane diluent. Our data show negligible effect of the organic phase on the radiolytic behavior of AHA compared to complementary single-phase experiments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Modeling Advanced Strippers for CO2 Capture from Gas-Fired Power Plants using Aqueous Piperazine

Energy performance of 5 m piperazine was evaluated with an advanced stripper at the pilot scale, accounting for heat loss. Modeling studies indicated that heat loss at locations other than the heat source impacted the heat duty. For strippers with excess packing, the column was the most important source of heat loss, and values as low as 0.03 GJ/hr can cause pinch and reabsorption of CO2. Solvents like 5 m PZ are more affected by heat loss in the column due to a top-side temperature pinch at high lean loading. Heat loss impacts NGCC CO2 capture more than coal-based CO2 capture. Surface temperature measurements pilot plants showed that heat loss was 50-75% controlled by natural convection. Measured heat loss was correlated with steam flowrate and wind speed and ranged from 8126 to 219668 Btu/hr, representing 35% of the measured heat rate on average. Net heat duty linearly varied with CO2 removal at low lean loading and was similar for coal and NGCC conditions at fixed removal. At 90% removal, net heat duty was about 2.5 GJ/t with 4 and 12% CO2 in the flue gas. 7 At NGCC conditions, strippers with finite packing can benefit from a flashing feed to the top of the column by using a hot bypass. A flashing feed was linked to a reduction in irreversibility of the stripper from temperature driving forces. It also reduces heat duty by up to 6% at fixed packing height and reduces packing requirement for a fixed steam heater size compared to a warm bypass. Lean loading and lean solvent rate were effective handles to maximize profitability of a fixed stripper design at low gas price. High ambient temperature operation can benefit from low pressure stripping to about 0.18 lean loading at 150 ℃ to maintain the cyclic capacity at reduced rich loading. At low gas price, the capture plant was able to maximize profitability even with a high heat duty of 2.7-3.1 GJ/t at a lean loading of 0.2-0.22 mol/mol. Heat recovery by partial water vapor condensation in a gas-liquid exchanger can be replaced by a direct contact condenser (DCC). The DCC improved gas cooling and reduced heat duty compared to the CO2 exchanger at 0.2 lean loading. The DCC when used with a 150 ℃/5.5 bar stripper can reduce the cost of capture compared to the base case by $3- 4/tonne at 15 ft of packing (optimum) but increases cost of capture by $6/tonne with a 120 ℃/2 bar stripper and 10 ft of packing (optimum). The DCC can work effectively with a solvent with a high heat of absorption and thermal stability.

Suresh Babu, Athreya↗

A global anthropogenic emission inventory of atmospheric pollutants from sector- and fuel-specific sources (1970–2017): an application of the Community Emissions Data System (CEDS)

Global anthropogenic emission inventories remain vital for understanding the sources of atmospheric pollution and the associated impacts on the environment, human health, and society. Rapid changes in today's society require that these inventories provide contemporary estimates of multiple atmospheric pollutants with both source sector and fuel type information to understand and effectively mitigate future impacts. To fill this need, we have updated the open-source Community Emissions Data System (CEDS) (Hoesly et al., 2019) to develop a new global emission inventory, CEDSGBD-MAPS. This inventory includes emissions of seven key atmospheric pollutants (NOx; CO; SO2; NH3; non-methane volatile organic compounds, NMVOCs; black carbon, BC; organic carbon, OC) over the time period from 1970–2017 and reports annual country-total emissions as a function of 11 anthropogenic sectors (agriculture; energy generation; industrial processes; on-road and non-road transportation; separate residential, commercial, and other sectors (RCO); waste; solvent use; and international shipping) and four fuel categories (total coal, solid biofuel, the sum of liquid-fuel and natural-gas combustion, and remaining process-level emissions). The CEDSGBD-MAPS inventory additionally includes monthly global gridded (0.5°?×?0.5°) emission fluxes for each compound, sector, and fuel type to facilitate their use in earth system models. CEDSGBD-MAPS utilizes updated activity data, updates to the core CEDS default scaling procedure, and modifications to the final procedures for emissions gridding and aggregation. Relative to the previous CEDS inventory (Hoesly et al., 2018), these updates extend the emission estimates from 2014 to 2017 and improve the overall agreement between CEDS and two widely used global bottom-up emission inventories. The CEDSGBD-MAPS inventory provides the most contemporary global emission estimates to date for these key atmospheric pollutants and is the first to provide global estimates for these species as a function of multiple fuel types and source sectors. Dominant sources of global NOx and SO2 emissions in 2017 include the combustion of oil, gas, and coal in the energy and industry sectors as well as on-road transportation and international shipping for NOx. Dominant sources of global CO emissions in 2017 include on-road transportation and residential biofuel combustion. Dominant global sources of carbonaceous aerosol in 2017 include residential biofuel combustion, on-road transportation (BC only), and emissions from the waste sector. Global emissions of NOx, SO2, CO, BC, and OC all peak in 2012 or earlier, with more recent emission reductions driven by large changes in emissions from China, North America, and Europe. In contrast, global emissions of NH3 and NMVOCs continuously increase between 1970 and 2017, with agriculture as a major source of global NH3 emissions and solvent use, energy, residential, and the on-road transport sectors as major sources of global NMVOCs. Due to similar development methods and underlying datasets, the CEDSGBD-MAPS emissions are expected to have consistent sources of uncertainty as other bottom-up inventories. The CEDSGBD-MAPS source code is publicly available online through GitHub: https://github.com/emcduffie/CEDS/tree/CEDS_GBD-MAPS (last access: 1 December 2020). The CEDSGBD-MAPS emission inventory dataset (both annual country-total and monthly global gridded files) is publicly available under https://doi.org/10.5281/zenodo.3754964 (McDuffie et al., 2020c).

Mcduffie, Erin↗

Catalytic Reduction of Graphene Oxide Membranes and Water Selective Channel Formation in Water–Alcohol Separations

Graphene oxide (GO) is a promising membrane system for chemical separation applications due to its 2-D nanofluidics properties and an ability to control interplanar spacing for selectivity. The permeance of water, methanol (MeOH) and isopropyl alcohol (IPA) through 5 µm thick membranes was found to be 0.38 ± 0.15, 0.33 ± 0.16 and 0.42 ± 0.31 LMH/bar (liter/m2·h·bar), respectively. Interestingly, the permeance of a water–alcohol mixture was found to be dramatically lower (~0.01 LMH/bar) than any of its components. Upon removing the solvent mixture, the transmembrane flux of the pure solvent was recovered to near the original permeance. The interlayer space of a dried GO membrane was found to be 8.52 Å, which increased to 12.19 Å. 13.26 Å and 16.20 Å upon addition of water, MeOH and IPA. A decrease in d-space, about 2 Å, was consistently observed when adding alcohol to water wetted GO membrane and an optical color change and reduction in permeance. A newly proposed mechanism of a partial reduction of GO through a catalytic reaction with the water–alcohol mixture is consistent with experimental observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methods and systems for the electrochemical reduction of carbon dioxide using switchable polarity materials

A method of electrochemically reducing CO2 comprises introducing a first feed stream comprising H2O to a positive electrode of an electrolysis cell comprising the positive electrode, a negative electrode, and a proton conducting membrane. A second feed stream comprising a solvent and a non polar form of a switchable polarity material is directed into a CO2 capture apparatus. A third feed stream comprising CO2 is directed into the CO2 capture apparatus to interact with the second feed stream and form a first product stream comprising the solvent and a polar form of the switchable polarity material. The first product stream is introduced to the negative electrode. A potential difference is applied between the positive electrode and the negative electrode to convert the polar form of the switchable polarity material into CO2 and the non-polar form and to form products from the CO2 and the solvent. A CO2 treatment system is also described.

Lister, Tedd E.↗

Theory-Enabled High-Throughput Screening of Ion Dissociation Explains Conductivity Enhancements in Diluted Ionic Liquid Mixtures

The growing demand for room-temperature ionic liquids (RTILs) for energy applications necessitates the development of an efficient screening platform. Here, in this study, we successfully developed a fully automated high-throughput RTIL screening platform specifically designed for assessing ionic conductivity. By utilizing the 96 wells of a microtiter plate as individual electrolysis cells, we measured the ionic conductivity of 22 different RTILs, encompassing various combinations of cations and anions, and benchmarked the values with existing literature. We also employed the screening platform to investigate the conductivities of RTIL mixtures with a nonaqueous solvent, ethylene glycol (EG). Specific combinations of RTILs with EG result in approximately 200% enhancement in the conductivity values compared to the pure RTILs. To understand the underlying mechanisms responsible for this enhancement, we developed a theoretical framework for ionic conductivity that considers factors such as the degree of dissociation, viscous forces, and molal volume of the RTIL-EG mixtures. The optimized electrolyte mixture was then employed in the migration-assisted moisture gradient (MAMG) CO 2 capture process to study the effects of improved ionic conductivity on the energy efficiency of the process. Notably, the enhanced conductivity of the RTIL-EG mixture led to a nearly 50% reduction in energy consumption for capturing CO 2 . These outcomes highlight the effectiveness of our strategy in screening RTILs and improving existing processes. Moreover, this fully automated high-throughput setup, combined with the developed theoretical framework, provides a comprehensive platform for screening and studying RTIL mixtures with different solvents, enabling their application in various fields.

25 ENERGY STORAGE↗

Water-Based Pressure Sensitive Paint

Preparation and performance of a water-based pressure sensitive paint (PSP) is described. A water emulsion of an oxygen permeable polymer and a platinum porphyrin type luminescent compound were dispersed in a water matrix to produce a PSP that performs well without the use of volatile, toxic solvents. The primary advantages of this PSP are reduced contamination of wind tunnels in which it is used, lower health risk to its users, and easier cleanup and disposal. This also represents a cost reduction by eliminating the need for elaborate ventilation and user protection during application. The water-based PSP described has all the characteristics associated with water-based paints (low toxicity, very low volatile organic chemicals, and easy water cleanup) but also has high performance as a global pressure sensor for PSP measurements in wind tunnels. The use of a water-based PSP virtually eliminates the toxic fumes associated with the application of PSPs to a model in wind tunnels.

Oglesby, Donald M.↗

Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. Here, we demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents.

09 BIOMASS FUELS↗

Strain-Modulated Platinum–Palladium Nanowires for Oxygen Reduction Reaction

Electrocatalytic activity of alloy nanocatalytsts can be manipulated effectively by tuning their physical properties (ensemble, geometric, and ligand effects) to afford optimal surface structure and compositions for proton exchange membrane fuel cell (PEMFC) application. Herein, highly catalytic platinum-palladium nanowires (Pt n Pd 100-n NWs) with a subtle lattice strain and Boerdijk-Coxeter helix type morphology are synthesized through a surfactant-free, thermal single phase solvent method. X-ray diffraction results show that Pt n Pd 100-n NWs are exposed through the (111) facets and their shrinking or expanding lattice parameters can be modulated by the alloy compositions. Electrochemical results reveal that their high catalytic activity correlates with the lattice shrinking, facets, and bimetallic compositions, showing higher activity when the ratio of Pt and Pd is similar to ~78:22, which is further supported by DFT results. Compared to the nanoparticle type platinum-palladium alloyed catalysts with similar metal compositions (Pt n Pd 100-n NPs), the Pt n Pd 100-n NWs exhibit significantly improved electrocatalytic activity and stability for the oxygen reduction reaction. Our findings open new strategies to design the highly active and stable alloy nanocatalysts with controllable compositions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Proton-Responsive Ligands Promote CO 2 Capture and Accelerate Catalytic CO 2 /HCO 2 – Interconversion

The synthesis and investigation of [Rh(DHMPE) 2 ][BF 4 ] (1) are reported. 1 features proton-responsive 1,2-bis[(dihydroxymethyl)phosphino]ethane (DHMPE) ligands, which readily capture CO 2 from atmospheric sources upon deprotonation. The protonation state of the DHMPE ligand was observed to have a significant impact on the catalytic reactivity of 1 with CO 2 . Deprotonation and CO 2 binding to 1 result in a ∼10-fold rate enhancement in catalytic degenerate CO 2 reduction with formate, monitored by 12 C/ 13 C isotope exchange between H 12 CO 2 – and 13 CO 2 . Studies performed using a similar complex lacking the hydroxyl ligand functionality ([Rh(DEPE) 2 ][BF 4 ] where DEPE = 1,2-bis(diethylphosphino)ethane) do not show the same rate enhancements when base is added. Based upon the cation-dependent activity of the catalyst, Eyring analysis, and cation sequestration experiments, CO 2 binding to 1 is proposed to facilitate preorganization of formate/CO 2 in the transition state via ligand-based encapsulation of Na + or K + cations to lower the activation energy and increase the observed catalytic rate. Incorporation of proton-responsive DHMPE ligands provides a unique approach to accelerate the kinetics of catalytic CO 2 reduction to formate.

Anions↗

Functionalized Polymersomes from a Polyisoprene-Activated Polyacrylamide Precursor

Self-assembled polymer nanoparticles have tremendous potential in biomedical and environmental applications. For all applications, tailored polymer chemistries are critical. In this study, we demonstrate a precursor approach in which an activated, organic solvent-soluble block polymer precursor is modified through mild postpolymerization modifications to access new polymer structures. We synthesized and characterized poly(isoprene)-block-poly(di-Boc acrylamide) diblock polymers. This activated-acrylamide-based polymer was then reacted with amines or reductants in the absence of catalysts to yield the hydrophilic blocks polyacrylamide, poly(hydroxypropylene), and poly(N-ethyl acrylamide). The resulting amphiphilic block polymers self-assembled in water to form polymersomes, as confirmed by cryo-electron microscopy and confocal microscopy. The approach also enables simple functionalization with specialized ligands, which we demonstrated by tagging polymers with an amino-fluorophore and imaging by confocal microscopy. Here, we expect that the methodologies established in this study will open doors to new and useful solution nanostructures with surface chemistries that can be optimized for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Open Circuit Potential Method for Thermodynamic Hydricity Measurements of Metal Hydrides

Metal hydrides are prevalent in many catalytic reactions, and thermodynamic hydricity has emerged as a useful parameter for understanding and predicting key hydride transfer steps with these intermediates. An open circuit potentiometry method for determining the hydricity of metal hydrides with a single thermodynamic parameter is reported. The open circuit potential (OCP) of a solution containing a metal hydride and its conjugate hydride acceptor, along with a conjugate acid/base pair, is coupled with known values for the acid pK a and H + /H – reduction potential to determine the hydricity. Here, the reliability of the method was established by using potentiometry to obtain the hydricity of three hydride complexes with varying supporting ligands and transition metal elements in acetonitrile solvent, all within error of previously reported values. Advantages and drawbacks of this method are discussed, and a recommended workflow for practitioners is introduced.

Anions↗

Use of radiation in preparative chemistry

A summary and updating of previous work on the use of radiation chemistry for the preparation of pure materials are presented. Work was chiefly concerned with the reduction of metal salts in solution to the free metal using 2 MeV electrons. Metals deposited from aqueous solution are copper, silver, zinc, cadmium, thallium, tin, lead, antimony, iron, nickel, cobalt, and palladium. Dry organic solvents were evaluated for the deposition of metals based on a study involving deposition of antimony from soltions of antimony (III) chloride. The use of organic liquids for the preparation of anhydrous metal halides is also presented. Reaction mechanisms for both organic liquids and aqueous system are discussed.

Philipp, W. H.↗

Transfer learning of memory kernels for transferable coarse-graining of polymer dynamics

The present work concerns the transferability of coarse-grained (CG) modeling in reproducing the dynamic properties of the reference atomistic systems across a range of parameters. In particular, we focus on implicit-solvent CG modeling of polymer solutions. The CG model is based on the generalized Langevin equation, where the memory kernel plays the critical role in determining the dynamics in all time scales. Thus, we propose methods for transfer learning of memory kernels. The key ingredient of our methods is Gaussian process regression. By integration with the model order reduction via proper orthogonal decomposition and the active learning technique, the transfer learning can be practically efficient and requires minimum training data. Through two example polymer solution systems, we demonstrate the accuracy and efficiency of the proposed transfer learning methods in the construction of transferable memory kernels. The transferability allows for out-of-sample predictions, even in the extrapolated domain of parameters. Built on the transferable memory kernels, the CG models can reproduce the dynamic properties of polymers in all time scales at different thermodynamic conditions (such as temperature and solvent viscosity) and for different systems with varying concentrations and lengths of polymers.

Ma, Zhan↗

Reactive CO 2 capture and mineralization of magnesium hydroxide to produce hydromagnesite with inherent solvent regeneration

Valorization of multiple low value streams including CO 2 emissions and magnesium-hydroxide bearing mine tailings to produce magnesium carbonate through reactive CO 2 capture and mineralization provides a less explored opportunity to manage several gigatons of CO 2 emissions. To resolve the feasibility of converting magnesium hydroxide to magnesium carbonate through reactive CO 2 capture and mineralization, CO 2 capture solvents such as sodium glycinate are harnessed to capture CO 2 and react directly with Mg(OH) 2 to produce hydromagnesite (Mg 5 [(CO 3 )4(OH) 2 ]·4H 2 O). This approach eliminates the energy-intensive step of producing high purity CO 2 associated with regenerating the solvent, and redissolving CO 2 to produce magnesium carbonate. Interestingly, while temperatures below 50 °C facilitate CO 2 capture, the mineralization kinetics are slow. However, at higher temperatures, accelerated carbon mineralization is favored by the faster kinetics of Mg(OH) 2 dissolution and precipitation of magnesium carbonate. Reacting Mg(OH) 2 at 90 °C with 15 wt% solids in the presence of 2.5 M sodium glycinate after 3 hours under well-stirred conditions results in an extent of carbon mineralization of 75.5%. The theoretical maximum extent of carbon mineralization when hydromagnesite is formed is 80%. Pre-loading CO 2 on the solvent is also an effective approach to ensure that sufficient CO2 is available for reactive CO 2 capture and mineralization, particularly when dilute CO 2 and N 2 mixtures are used. Higher extents of carbon mineralization are associated with an increase in the particle size and a reduction in the cumulative pore volume. These insights unlock the feasibility of harnessing reactive CO 2 capture and mineralization as a pathway to convert magnesium-hydroxide bearing resources into industrially relevant magnesium carbonate products.

Reactive CO2↗

Water and Solute Activities Regulate CO 2 Reduction in Gas-Diffusion Electrodes

Electrolysis of CO 2 at gas-diffusion electrodes (GDEs) has typically been limited by the supply of gas to the electrocatalyst, overshadowing the importance of the supply of water. However, at high current densities that approach 1 A cm –2 , where the electrolyte becomes highly concentrated in the catalyst layer of a GDE, the activity of water and solutes deviate from their bulk dilute solution values, potentially slowing reaction rates and changing reaction equilibrium potentials. In addition, as flow plates for the gas stream are introduced to enable larger electrodes and high single pass conversion of CO 2 to product, variations in the gas composition will become important. By drawing upon literature for the oxygen reduction reaction (ORR), here we explain how to account for these effects in future modeling and experimental work, with particular attention to accurate use of the Nernst equation for electrode potentials and the Arrhenius equation for reaction rates. Specifically, using measurements of KOH solvent and solute activity reported in literature, and assuming the second protonation of CO 2 by water as the rate-determining step, we show the Nernst equation dilute-solution approximation of the CO 2 to CO equilibrium potential to be accurate below 5 M KOH, but it has a 74 mV error when increasing the concentration up to 10 M KOH. Finally, a simple one-dimensional model of a serpentine flow-field on a GDE demonstrated that a reactor with constant pressure of 1 bar and 1 A cm –2 at the inlet had only ~0.3 A cm –2 at the outlet for a conversion in CO 2 partial pressure from 0.90 to 0.48 bar, showing the significant practical implications of this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗