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DOE OSTI2012

A GAS-PHASE FORMATION ROUTE TO INTERSTELLAR TRANS-METHYL FORMATE

The abundance of methyl formate in the interstellar medium has previously been underpredicted by chemical models. Additionally, grain surface chemistry cannot account for the relative abundance of the cis- and trans-conformers of methyl formate, and the trans-conformer is not even formed at detectable abundance on these surfaces. This highlights the importance of studying formation pathways to methyl formate in the gas phase. The rate constant and branching fractions are reported for the gas-phase reaction between protonated methanol and formic acid to form protonated trans-methyl formate and water as well as adduct ion: Rate constants were experimentally determined using a flowing afterglow-selected ion flow tube apparatus at 300 K and a pressure of 530 mTorr helium. The results indicate a moderate overall rate constant of (3.19 {+-} 0.39) Multiplication-Sign 10{sup -10} cm{sup 3} s{sup -1} ({+-} 1{sigma}) and an average branching fraction of 0.05 {+-} 0.04 for protonated trans-methyl formate and 0.95 {+-} 0.04 for the adduct ion. These experimental results are reinforced by ab initio calculations at the MP2(full)/aug-cc-pVTZ level of theory to examine the reaction coordinate and complement previous density functional theory calculations. This study underscores the need for continued observational studies of trans-methyl formate and for the exploration of other gas-phase formation routes to complex organic molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

HCOOH Decomposition on Sub-Nanometer Pd 6 Cluster Catalysts: The Effect of Defective Boron Nitride Supports Through First Principles

The catalytic properties of a hexagonal boron nitride- (h-BN) supported Pd 6 sub-nanometer cluster in the context of formic acid (HCOOH) decomposition were studied by means of periodic Density Functional Theory (DFT) calculations. The effect of support defectivity – boron (h-B v N) and nitrogen (h-BN v ) monovacancies – on the competition between the formate (HCOO)- and carboxyl (COOH)-mediated decomposition pathways was analyzed. Defects are responsible for charge-transfer leading to a positively or negatively charged cluster, and open new reactive channels in which vacancy-mediated dehydrogenation pathways can occur. Pd 6 cluster reconstructions, induced by the adsorption of reaction intermediates and by the presence of monovacancies in the support, greatly stabilize the formation of CO from COOH, which could drastically decrease the selectivity towards hydrogen production. Here, a simplified descriptor-based analysis, based on selected thermochemical quantities calculated on charged cluster models, suggests that Pd 6 sub-nanometer clusters supported on pristine h-BN and h-BN v can be more selective than Pd 6 supported on defective h-B v N towards HCOOH dehydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

THE ORIGIN OF COMPLEX ORGANIC MOLECULES IN PRESTELLAR CORES

Complex organic molecules (COMs) have been detected in a variety of environments including cold prestellar cores. Given the low temperatures of these objects, these detections challenge existing models. We report here new observations toward the prestellar core L1544. They are based on an unbiased spectral survey of the 3 mm band at the IRAM 30 m telescope as part of the Large Program ASAI. The observations allow us to provide a full census of the oxygen-bearing COMs in this source. We detected tricarbon monoxide, methanol, acetaldehyde, formic acid, ketene, and propyne with abundances varying from 5 × 10{sup –11} to 6 × 10{sup –9}. The non-LTE analysis of the methanol lines shows that they are likely emitted at the border of the core at a radius of ∼8000 AU, where T ∼ 10 K and n {sub H{sub 2}} ∼2 × 10{sup 4} cm{sup –3}. Previous works have shown that water vapor is enhanced in the same region because of the photodesorption of water ices. We propose that a non-thermal desorption mechanism is also responsible for the observed emission of methanol and COMs from the same layer. The desorbed oxygen and a small amount of desorbed methanol and ethene are enough to reproduce the abundances of tricarbon monoxide, methanol, acetaldehyde, and ketene measured in L1544. These new findings open the possibility that COMs in prestellar cores originate in a similar outer layer rather than in the dense inner cores, as previously assumed, and that their formation is driven by the non-thermally desorbed species.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2011

Final Technical Report: Effects of Impurities on Fuel Cell Performance and Durability

The main objectives of this project were to investigate the effect of a series of potential impurities on fuel cell operation and on the particular components of the fuel cell MEA, to propose (where possible) mechanism(s) by which these impurities affected fuel cell performance, and to suggest strategies for minimizing these impurity effects. The negative effect on Pt/C was to decrease hydrogen surface coverage and hydrogen activation at fuel cell conditions. The negative effect on Nafion components was to decrease proton conductivity, primarily by replacing/reacting with the protons on the Bronsted acid sites of the Nafion. Even though already well known as fuel cell poisons, the effects of CO and NH3 were studied in great detail early on in the project in order to develop methodology for evaluating poisoning effects in general, to help establish reproducibility of results among a number of laboratories in the U.S. investigating impurity effects, and to help establish lower limit standards for impurities during hydrogen production for fuel cell utilization. New methodologies developed included (1) a means to measure hydrogen surface concentration on the Pt catalyst (HDSAP) before and after exposure to impurities, (2) a way to predict conductivity of a Nafion membranes exposed to impurities using a characteristic acid catalyzed reaction (methanol esterification of acetic acid), and, more importantly, (3) application of the latter technique to predict conductivity on Nafion in the catalyst layer of the MEA. H2-D2 exchange was found to be suitable for predicting hydrogen activation of Pt catalysts. The Nafion (ca. 30 wt%) on the Pt/C catalyst resides primarily on the external surface of the C support where it blocks significant numbers of micropores, but only partially blocks the pore openings of the meso- and macro-pores wherein lie the small Pt particles (crystallites). For this reason, even with 30 wt% Nafion on the Pt/C, few Pt sites are blocked and, hence, are accessible for hydrogen activation. Of the impurities studied, CO, NH3, perchloroethylene (also known as tetrachloroethylene), tetrahydrofuran, diborane, and metal cations had significant negative effects on the components in a fuel cell. While CO has no effect on the Nafion, it significantly poisons the Pt catalyst by adsorbing and blocking hydrogen activation. The effect can be reversed with time once the flow of CO is stopped. NH3 has no effect on the Pt catalyst at fuel cell conditions; it poisons the proton sites on Nafion (by forming NH4+ cations), decreasing drastically the proton conductivity of Nafion. This poisoning can slowly be reversed once the flow of NH3 is stopped. Perchloroethylene has a major effect on fuel cell performance. Since it has little/no effect on Nafion conductivity, its poisoning effect is on the Pt catalyst. However, this effect takes place primarily for the Pt catalyst at the cathode, since the presence of oxygen is very important for this poisoning effect. Tetrahydrofuran was shown not to impact Nafion conductivity; however, it does affect fuel cell performance. Therefore, its primary effect is on the Pt catalyst. The effect of THF on fuel cell performance is reversible. Diborane also can significant affect fuel cell performance. This effect is reversible once diborane is removed from the inlet streams. H2O2 is not an impurity usually present in the hydrogen or oxygen streams to a fuel cell. However, it is generated during fuel cell operation. The presence of Fe cations in the Nafion due to system corrosion and/or arising from MEA production act to catalyze the severe degradation of the Nafion by H2O2. Finally, the presence of metal cation impurities (Na+, Ca 2+, Fe3+) in Nafion from MEA preparation or from corrosion significantly impacts its proton conductivity due to replacement of proton sites. This effect is not reversible. Hydrocarbons, such as ethylene, might be expected to affect Pt or Nafion but do not at a typical fuel cell temperature of 80oC. In the presence of large quantities of hydrogen on the anode side, ethylene is converted to ethane which is very nonreactive. More surprisingly, even more reactive hydrocarbons such as formic acid and acetaldehyde do not appear to react enough with the strong Bronsted acid sites on Nafion at such low temperatures to affect Nafion conductivity properties. These results clearly identify a number of impurities which can have a detrimental impact on fuel cell performance, although some are reversible. Obviously, fuel cells exposed to impurities/poisons which are reversible can recover their original performance capabilities once the impurity flow is stopped. Impurities with irreversible effects should be either minimized in the feed streams, if possible, or new catalytic materials or ion conductors will need to be used to minimize their impact.

08 HYDROGEN↗

DOE OSTI2014

Data Analysis and Model Validation (2013 CEF Run - Phase 1)

Phase 1 of the 2013 Cold cap Evaluation Furnace (CEF) test was completed on June 3, 2013 after a 5-day round-the-clock feeding and pouring operation. The main goal of the test was to characterize the CEF offgas produced from a nitric-formic acid flowsheet feed and confirm whether the CEF platform is capable of producing scalable off-gas data necessary for the revision of the DWPF melter off-gas flammability model; the revised model will be used to define new safety controls on the key operating parameters for the nitric-glycolic acid flowsheet feeds including total organic carbon (TOC). Whether the CEF off-gas data were scalable for the purpose of predicting the potential flammability of the DWPF melter exhaust was determined by comparing the predicted H 2 and CO concentrations using the current DWPF melter off-gas flammability model to those measured during Phase 1; data were deemed scalable if the calculated fractional conversions of TOC-to-H 2 and TOC-to-CO at varying melter vapor space temperatures were found to trend and further bound the respective measured data with some margin of safety. Being scalable thus means that for a given feed chemistry the instantaneous flow rates of H 2 and CO in the DWPF melter exhaust can be estimated with some degree of conservatism by multiplying those of the respective gases from a pilot-scale melter by the feed rate ratio. This report documents the results of the Phase 1 data analysis and the necessary calculations performed to determine the scalability of the CEF off-gas data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2015

HCOOH decomposition on Pt(111): A DFT study

Formic acid (HCOOH) decomposition on transition metal surfaces is important for hydrogen production and for its electro-oxidation in direct HCOOH fuel cells. HCOOH can decompose through dehydrogenation leading to formation of CO 2 and H 2 or dehydration leading to CO and H 2 O; because CO can poison metal surfaces, dehydrogenation is typically the desirable decomposition path. Here we report a mechanistic analysis of HCOOH decomposition on Pt(111), obtained from a plane wave density functional theory (DFT-PW91) study. We analyzed the dehydrogenation mechanism by considering the two possible pathways involving the formate (HCOO) or the carboxyl (COOH) intermediate. We also considered several possible dehydration paths leading to CO formation. We studied HCOO and COOH decomposition both on the clean surface and in the presence of other relevant co-adsorbates. The results suggest that COOH formation is energetically more difficult than HCOO formation. In contrast, COOH dehydrogenation is easier than HCOO decomposition. Here, we found that CO 2 is the main product through both pathways and that CO is produced mainly through the dehydroxylation of the COOH intermediate.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Copper-Doped Tin Oxides Supported on Mesoporous Carbon Xerogel for Boosting the Electrochemical Reduction of CO 2 to Formate in Bicarbonate Solution Coupled with CO 2

The electrochemical reduction of CO 2 into valuable products at mild reaction conditions and using cheap renewable electrical energy are goals to sustain a low-carbon economy. Among the various CO 2 reduction reaction products, formic acid (FA) has received significant attention because of its low Gibbs free energy input requirement and the simple reduction reaction involving the transfer of 2 electrons and 2 protons. In this work, a copper-doped tin oxide catalyst supported on a mesoporous carbon xerogel was shown to enhance the electrochemical reduction of CO 2 to formate in a bicarbonate solution coupled with CO 2 . We observed that the synergistic SnCu oxides enhance the selectivity toward formate from 58.6% for Sn oxide and 28.7% for Cu oxide to over 71.2% for the SnCu oxides. The observed rate of formate production with SnCu oxide was 2.8 times higher compared to the rate of Cu oxide and about 1.5 times higher than with the Sn oxide catalyst. Our results reveal that selectivity for formate comes partly from the electrolysis of the bicarbonate solution and partly from continuous CO 2 gas purged into the solution. The contribution from the electrolysis of bicarbonate solution ranges from 15% to 40% when the concentration of bicarbonate solution ranges from 100 mM to 1 M. Chronoamperometric measurements for stability revealed that Cu oxide and Sn oxide showed stable current density for less than 30 h while under the same conditions, the stable current density was observed for more than 50 h with SnCu oxide catalyst. Additionally, the selectivity toward formate increased by 6% when the reactor pressure was increased from near ambient pressure to 4 psig. Our lab-scale electrochemical cell with SnCu oxide supported on the mesoporous carbon xerogel enhances the CO 2 solubility, minimizes the precipitation of salts that can degrade the catalytic performance, and suppresses the competitive hydrogen evolution reaction, demonstrating the feasibility of using our catalyst and system for the electrochemical conversion of CO 2 into formate with high selectivity, productivity, and stability. Furthermore, this could have significant implications for the mitigation of CO 2 emissions and the development of a sustainable chemical industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Photo- and gas-tuned, reversible thermoelectric properties and anomalous photo-thermoelectric effects of platinum-loaded tungsten trioxide

We report the photo- and gas-controllable properties of platinum-loaded tungsten trioxide (Pt/WO{sub 3}), which is of interest for developing practical applications of WO{sub 3} as well as for interpreting such phenomena from scientific viewpoints. Here, a Pt/WO{sub 3} thin film generated a thermoelectric power due to the ultraviolet-light-induced band-gap excitation (photochromic (PC) reaction) and/or dark storage in formic acid vapor (gaschromic (GC) reaction) in the absence of O{sub 2}, resulting from the generation of W{sup 5+} ions. After such chromic reactions, the electrical conductivity (σ) is increased, whereas the absolute value of the Seebeck coefficient (S) is decreased. The changes in σ and S and their rate of change for consistency increased in the order of: during the PC reaction < during the GC reaction < during simultaneous PC and GC reactions. The opposite behaviors, a decrease in σ and an increase in S, were exhibited by Pt/WO{sub 3} in the presence of O{sub 2} after dark storage or visible-light irradiation. This reversible cycle could be repeated. Moreover, anomalous, nontrivial photo-thermoelectric effects (a photoconductive effect (photoconductivity, σ{sub photo}) and a photo-Seebeck effect (photo-Seebeck coefficient, S{sub photo})) were also detected in response to the visible-light irradiation of Pt/WO{sub 3} in the absence of O{sub 2} after chromic reactions. Under visible-light irradiation, both σ{sub photo} and the absolute value of S{sub photo} are increased. After the irradiation, both values were decreased, that is, σ and the absolute value of S were smaller than σ{sub photo} and the absolute value of S{sub photo}, respectively. These effects are likely to be due to the photoinduced charge carriers and the accumulated electrons in Pt contributing to the increase in σ{sub photo}. In addition, electrons are extracted from the W{sup 5+} state, decreasing the number of W{sup 5+} in H{sub x}WO{sub 3} and thus contributing to the increase in S{sub photo}. After light irradiation, the accumulated electrons in Pt are returned to the energetically favorable W{sup 5+} state, and Pt/H{sub x}WO{sub 3} are returned to the initial state. Then both σ and S are decreased. The mechanisms of our anomalous, nontrivial photo-thermoelectric effects are presumed to be different from that involving the two-carrier contribution to the transport properties.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2020

Scale and Regionality of Nonelectric Markets for U.S. Nuclear Light Water Reactors

This study assesses existing and potential industries that could conceivably be directly coupled to existing nuclear reactors. The goal is to identify the scale, location, and accessibility of the candidate industrial-product markets, as well as process feedstocks that are available near the plants to establish new industries. For example, CO 2 as a feedstock can be combined with H 2 to produce formic acid (FA), transportation fuels, and lubricants. These new plants can be entirely supported with the heat and electricity provided by a nearby NPP. The potential demand for nonelectric industrial products was assessed by documenting current and possible growth of nonelectricity product markets considered. This assessment used DOE- and industry-supported tools, data, and projections to capture regional industrial market opportunities. Electricity-capacity markets that reward large and reliable generators, such as NPPs, were considered because the electricity market will likely continue to be an important revenue source to NPPs. The key is to balance the needs of energy customers so as to optimize revenue for the affiliated energy customers or partners. In most cases, flexible plant energy delivery and power generation for the grid will require either energy storage or a stock of intermediate products to sustain the industrial customers when the NPP dispatches electricity to the grid. A diverse mix of temperate regions with operating NPPs around the U.S.—representing a variety of operating markets, local generation mix, and seasonal climates—were chosen for this market study. Both current and future market opportunities for candidate industrial-product markets surrounding these NPPs were studied. Figure 2 illustrates the regions chosen for this study. The success of developing nonelectric industrial-product markets as alternative revenue-generating sources for LWRs depends, not only on demand from growing existing markets, such as petroleum refining and NH 3 production, but also on the development of new markets such as light-duty (LD) and heavy-duty (HD) hydrogen FCEVs, synfuels, chemical production, biofuels, metal refining, injection of hydrogen into NG pipelines for gas power-generating units, FA, polymers, and close-coupled industrial heat applications, all of which can significantly increase demand relative to current levels while decarbonizing energy sectors. This study also presents a sample analysis of the economics of hydrogen production in an area of Minnesota, considering the capital and operating costs of a hydrogen plant as well as the local market demand for hydrogen. It includes some assumptions on electricity-grid pricing, showing how hydrogen could be integrated with an NPP and be competitive with the incumbent hydrogen-production process, steam methane reforming (SMR). The objectives of this study include: Provide U.S. NPP operators a robust sampling of the market demand location, scale, and accessibility (including storage and transportation) of the wide variety of industrial-product choices that can be produced using nuclear thermal energy and electricity proximate to a subset of U.S. NPPs to inform the industry of the potential opportunity; show examples and trade-off analyses of how U.S. LWR operators can access these markets, including storage and transportation of industrial products to their intended markets; and present a general analysis example for one industrial product (hydrogen) in one region (Minnesota area), including production, storage, and transportation, to show how nuclear-hybrid integrated energy systems (IESs) could access local markets and improve the profitability of an NPP.

03 NATURAL GAS↗

DOE OSTI2014

ACTUAL WASTE TESTING OF GYCOLATE IMPACTS ON THE SRS TANK FARM

Glycolic acid is being studied as a replacement for formic acid in the Defense Waste Processing Facility (DWPF) feed preparation process. After implementation, the recycle stream from DWPF back to the high-level waste Tank Farm will contain soluble sodium glycolate. Most of the potential impacts of glycolate in the Tank Farm were addressed via a literature review and simulant testing, but several outstanding issues remained. This report documents the actual-waste tests to determine the impacts of glycolate on storage and evaporation of Savannah River Site high-level waste. The objectives of this study are to address the following: Determine the extent to which sludge constituents (Pu, U, Fe, etc.) dissolve (the solubility of sludge constituents) in the glycolate-containing 2H-evaporator feed. Determine the impact of glycolate on the sorption of fissile (Pu, U, etc.) components onto sodium aluminosilicate solids. The first objective was accomplished through actual-waste testing using Tank 43H and 38H supernatant and Tank 51H sludge at Tank Farm storage conditions. The second objective was accomplished by contacting actual 2H-evaporator scale with the products from the testing for the first objective. There is no anticipated impact of up to 10 g/L of glycolate in DWPF recycle to the Tank Farm on tank waste component solubilities as investigated in this test. Most components were not influenced by glycolate during solubility tests, including major components such as aluminum, sodium, and most salt anions. There was potentially a slight increase in soluble iron with added glycolate, but the soluble iron concentration remained so low (on the order of 10 mg/L) as to not impact the iron to fissile ratio in sludge. Uranium and plutonium appear to have been supersaturated in 2H-evaporator feed solution mixture used for this testing. As a result, there was a reduction of soluble uranium and plutonium as a function of time. The change in soluble uranium concentration was independent of added glycolate concentration. The change in soluble plutonium content was dependent on the added glycolate concentration, with higher levels of glycolate (5 g/L and 10 g/L) appearing to suppress the plutonium solubility. The inclusion of glycolate did not change the dissolution of or sorption onto actual-waste 2H-evaporator pot scale to an extent that will impact Tank Farm storage and concentration. The effects that were noted involved dissolution of components from evaporator scale and precipitation of components onto evaporator scale that were independent of the level of added glycolate.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS1984

The photochemistry of a remote marine stratiform cloud

The coupled gas- and aqueous-phase photochemistry of a stratiform cloud in a remote region of the marine atmosphere is investigated with a time-dependent box model. Both scavenging of ambient acidic aerosols and gases as well as aqueous-phase chemical reactions within droplets are found to be important sources of acidity to cloud water and can lead to pH levels in cloud water in the remote marine atmosphere well below 5.6. The major sources of acidity via aqueous-phase chemical reactions are the generation of sulfuric acid from dissolved SO2 and the generation of formic acid from dissolved formaldehyde. In both cases, aqueous-phase free radicals can play a significant role either directly by oxidizing dissolved SO2 and HCHO or indirectly by producing the aqueous-phase oxidant H2O2. The rate of SO2 conversion to sulfuric acid is sensitive to a variety of parameters including the accommodation or sticking coefficient for SO2, H2O2, HO2, and OH, the liquid water content, and the ambient levels of SO2, HNO3, and other acidic or basic gases. Because high levels of SO2 tend to deplete cloud water of H2O3, the possibility exists that the pH of precipitation in polluted regions will respond nonlinearly to reduced SO2 emissions.

Chameides, W. L.↗

DOE OSTI2016

Actual Waste Demonstration of the Nitric-Glycolic Flowsheet for Sludge Batch 9 Qualification

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) performs qualification testing to demonstrate that the sludge batch is processable. Testing performed by the Savannah River National Laboratory has shown glycolic acid to be effective in replacing the function of formic acid in the DWPF chemical process. The nitric-glycolic flowsheet reduces mercury, significantly lowers the catalytic generation of hydrogen and ammonia which could allow purge reduction in the Sludge Receipt and Adjustment Tank (SRAT), stabilizes the pH and chemistry in the SRAT and the Slurry Mix Evaporator (SME), allows for effective rheology adjustment, and is favorable with respect to melter flammability. In order to implement the new flowsheet, SRAT and SME cycles, designated SC-18, were performed using a Sludge Batch (SB) 9 slurry blended from SB8 Tank 40H and Tank 51H samples. The SRAT cycle involved adding nitric and glycolic acids to the sludge, refluxing to steam strip mercury, and dewatering to a targeted solids concentration. Data collected during the SRAT cycle included offgas analyses, process temperatures, heat transfer, and pH measurements. The SME cycle demonstrated the addition of glass frit and the replication of six canister decontamination additions. The demonstration concluded with dewatering to a targeted solids concentration. Data collected during the SME cycle included offgas analyses, process temperatures, heat transfer, and pH measurements. Slurry and condensate samples were collected for subsequent analysis

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2024

Intelligent Electrochemical Sensors for Precise Identification of Volatile Organic Compounds Enabled by Neural Network Analysis

The volatile organic compounds (VOCs) in a wide spectrum of categories were identified as biomarkers in aquatic environments, playing an important role in marine and freshwater ecology and global atmospheric chemistry. VOCs released from biofuel have also attracted increasing attention. Although the importance has been recognized, the portable detection and analysis methods of VOC in aquatic systems have not yet been well developed and understood. Here, in this work, we innovatively proposed an intelligent electrochemical sensing approach to classify and quantify VOCs in solution. Utilizing the cyclic voltammetry (CV) method with an ionic liquid (IL)-based electrolyte, we analyzed 50 μL samples of various VOC analytes, including acetic acid (AC), acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethanol, formaldehyde, formic acid, methanol, methyl formate (MF), toluene, and a formaldehyde-methanol mixture, along with deionized water (DI water). The generated voltammograms were subsequently analyzed using our uniquely designed and optimized 1-D convolutional neural network (1D-CNN). This deep-learning algorithm achieved a 99.09% accuracy in VOC classification validated through fivefold cross-validation and demonstrated an impressive 94.4% test accuracy for methanol detection within a 10 μL error range. For quantification, the system accurately categorized methanol volumes ranging from 0 to 50 μL in 10 μL increments, achieving a 98.18% accuracy. A notable linear correlation (R2 = 95.56%) was found between max current density at the oxidation peak and methanol volume, with the limit of detection (LOD) at 9.3 μL. Such a sensing method exhibits potential for portability, high accuracy, and generalization in the classification and quantification, ultimately reshaping the realm of VOC analysis in solution.

42 ENGINEERING↗

DOE OSTI2021

Modeling of Glycolate Destruction in the Recycle Collection Tank

The Savannah River Site’s DWPF is being upgraded with the introduction of the NG flowsheet. Glycolic acid has been shown to be a superior alternative to formic acid for sludge processing. The new flowsheet improves or maintains necessary parameters such as 1) reduction of mercury, 2) adjustment of feed rheology, 3) pH stability, and 4) adjustment of melter oxidation/reduction potential. Further, the use of glycolic acid virtually eliminates the potential for catalytic hydrogen generation in DWPF processing DWPF process condensates are collected and returned to the Savannah River Site (SRS) CSTF. The RCT collects off-gas condensate during chemical processing, vitrification, and other unit operations performed in DWPF and is the singular return vessel delivering recycle effluent back to CSTF. Each batch of recycle will have a small amount of glycolate from chemical processing and melter off-gas condensates. To avoid potential flammability issues due to thermolysis of glycolate in the CSTF, Savannah River National Laboratory (SRNL) provided to Savannah River Remediation (SRR) at their request a Task Technical and Quality Assurance Plan (TTQAP) to quantify and mitigate glycolate returns via DWPF’s recycle stream. The request included testing of a process to oxidize glycolate and other organic species that are responsible for hydrogen generation from thermolysis. Following that work SRR provided a Task Technical Request (TTR) that requested process modeling. In 2021 a TTQAP was issued to cover the modeling work. Modeling draws data from laboratory scale studies using chemical simulants and radioactive waste samples. Chemical kinetic modeling was performed to evaluate the feasibility of using sodium permanganate to destroy glycolate in the RCT. The results from the laboratory studies were summarized in a series of reports. Reference 9 is a report of lab scale processing of actual DWPF Slurry Mix Evaporate Condensate Tank (SMECT) and Offgas Condensate Tank (OGCT) samples in the SRNL Shielded Cells. Tests at caustic conditions demonstrated sodium permanganate was effective in converting glycolate to oxalate, and permanganate (Mn 7+ ) is reduced to manganate (Mn 6+ ) with no significant formation of carbon dioxide or carbonate. Equation (1) was found to best describe the observed reaction of glycolate with permanganate under nominal (60 to 145 mg/L in RCT) glycolate entrainment conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS1985

Determination of the viscosity number of thermoplastics in dilute solution; polyamides (PA)

This West German Standard presents a test used to determine the viscosity number of polyamides and copolyamides which are easily diluted in sulfuric acid, and for other polyamides which are less easily diluted in sulfuric acid, and which are diluted in m-cresol. As formic acid is often used in industry instead of sulfuric acid, this solvent is also presented as an alternative, however, sulfuric acid is preferred because of the thermodynamic solubility characteristics of the polyamides and the handling safety. In addition, it is shown which solvent should be used for each polyamide. Finally, determinations concerning the preparation of the samples are presented. Using the viscosity number, a determination of the molar mass of the polyamides is possible.

Source record↗

DOE OSTI2013

Simulated Waste Testing Of Glycolate Impacts On The 2H-Evaporator System

Glycolic acid is being studied as a total or partial replacement for formic acid in the Defense Waste Processing Facility (DWPF) feed preparation process. After implementation, the recycle stream from DWPF back to the high-level waste tank farm will contain soluble sodium glycolate. Most of the potential impacts of glycolate in the tank farm were addressed via a literature review, but several outstanding issues remained. This report documents the non-radioactive simulant tests impacts of glycolate on storage and evaporation of Savannah River Site high-level waste. The testing for which non-radioactive simulants could be used involved the following: the partitioning of glycolate into the evaporator condensate, the impacts of glycolate on metal solubility, and the impacts of glycolate on the formation and dissolution of sodium aluminosilicate scale within the evaporator. The following are among the conclusions from this work: Evaporator condensate did not contain appreciable amounts of glycolate anion. Of all tests, the highest glycolate concentration in the evaporator condensate was 0.38 mg/L. A significant portion of the tests had glycolate concentration in the condensate at less than the limit of quantification (0.1 mg/L). At ambient conditions, evaporator testing did not show significant effects of glycolate on the soluble components in the evaporator concentrates. Testing with sodalite solids and silicon containing solutions did not show significant effects of glycolate on sodium aluminosilicate formation or dissolution.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS1988

Atmospheric geochemistry of formic and acetic acids at a mid-latitude temperate site

Tropospheric concentrations of formic and acetic acids in the gas, the aerosol, and the rainwater phases were determined in samples collected 1-2 m above ground level at an open field site in eastern Virginia. These acids were found to occur principally (98 percent or above) in the gas phase, with a marked annual seasonality, averaging 1890 ppt for formate and 1310 ppt for acetate during the growing season, as compared to 695 ppt and 700 ppt, respectively, over the nongrowing season. The data support the hypothesis that biogenic emissions from vegatation are important sources of atmospheric formic and acetic acid during the local growing season. The same time trends were observed for precipitation, although with less defined seasonality. The relative increase of the acetic acid/formic acid ratio during the nongrowing season points to the dominance of anthropogenic inputs of acetic acid from motor vehicles and biomass combustion in the wintertime.

Talbot, R. W.↗

NASA NTRS1997

Large-Scale Distributions of Tropospheric Nitric, Formic, and Acetic acids Over the Westerm Pacific Basin During Wintertime

We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3 - 12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases less than 100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15 deg N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25 deg N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r(sup 2) = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r(sup 2) = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO, mixing ratios were several parts per billion by volume (ppbv), yielding relationships with 03 and N2O consistent with those previously reported for NO(y).

Talbot, R. W.↗