Oxidative degradation of bis(2,4,4-trimethylpentyl
Samples of bis(2,4,4-trimethylpentyl)dithiophosphi
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Infrared optical constants of H2O ice, amorphous nitric acid solutions, and nitric acid hydrates
We determined the infrared optical constants of nitric acid trihydrate, nitric acid dihydrate, nitric acid monohydrate, and solid amorphous nitric acid solutions which crystallize to form these hydrates. We have also found the infrared optical constants of H2O ice. We measured the transmission of infrared light throught thin films of varying thickness over the frequency range from about 7000 to 500/cm at temperatures below 200 K. We developed a theory for the transmission of light through a substrate that has thin films on both sides. We used an iterative Kramers-Kronig technique to determine the optical constants which gave the best match between measured transmission spectra and those calculated for a variety of films of different thickness. These optical constants should be useful for calculations of the infrared spectrum of polar stratospheric clouds.
Toon, Owen B.↗
Isotopically Tracking Nitrogen Oxides, Nitrous Acid, And Nitric Acid, Particulate Nitrate from Wildfire During FIREX-AQ
Wildfires are an important source of reactive nitrogen species including nitrogen oxides (NOx = NO + NO2) and nitrous acid (HONO), as well as products such as nitric acid (HNO3) and particulate nitrate (p-NO3-). These species have strongly influence air quality and climate. In summer of 2019 (July 25 —August 21), as part of the FIREX-AQ ground mission, we drove ~3000 miles and sampled smoke of different ages in both daytime and nighttime from 5 different wildfires in the western US. Using recently developed methods that have been validated in both laboratory and field settings, we conducted high time resolution collection of NOx, NO2, HONO, HNO3, and p-NO3- for off-line characterization of isotopic composition δ15N, δ18O and Δ17O (=δ17O−0.52 δ18O). δ15N serves as a potential tracer for tracking sources and reactive nitrogen cycling pathways, δ18O and Δ17O provide key information about oxidation pathways (i.e. O3 versus RO2). Our measured δ15N for HONO ranges from -4.9‰ to +5.2‰ and -8‰ to +5.2‰ respectively, in the majority overlapping with our prior lab controlled burning results, which suggests the capability of δ15N for tracing the biomass burning emissions against other sources including vehicular emissions and soil emissions. In addition, our measurements show δ18O and Δ17O for NO2 and HONO vary significantly day vs night, as well as in young smoke vs aged smoke, likely reflecting different oxidizing mechanisms under different smoke conditions. Preliminary results of isotopic signatures of all the above reactive nitrogen species will be presented, and their relationships will be explored to identify wildfire derived reactive nitrogen source signatures and to constrain atmospheric processing pathways (e.g. secondary formation of HONO) for different fires under various smoke conditions depending on fuel types, fire conditions and meteorological conditions.
Jiajue Chai↗
Liquid-Phase Heat-Release Rates of the Systems Hydrazine-Nitric Acid and Unsymmetrical Dimethylhydrazine-Nitric Acid
The initial rates of heat release produced by the reactions of hydrazine and unsymmetrical dimethylhydrazine with nitric acid were determined in a bomb calorimeter under conditions of forced mixing. Fuel-oxidant weight ratio and injection velocity were varied. The rate of heat release apparently depended on the interfacial area between the propellants. Above a narrow range of injection velocities representing a critical amount of interfacial area, the rates reached a maximum and were almost constant with injection velocity. The maximum rate for hydrazine was about 70 percent greater than that for unsymmetrical dimethylhydrazine. The total heat released did not vary with mixture ratio over the range studied.
Somogyi, Dezso↗
Nitric acid in polar stratospheric clouds - Similar temperature of nitric acid condensation and cloud formation
As shown independently by two different techniques, nitric acid aerosols and polar stratospheric clouds (PSCs) both form below similar threshold temperatures. This supports the idea that the PSC particles involved in chlorine activation and ozone depletion in the winter polar stratosphere are composed of nitric acid. One technique used to show this is the inertial impaction of nitric acid aerosols using an Er-2 aircraft; the other method is remote sensing of PSCs by the Stratospheric Aerosol Measurement (SAM II) satellite borne optical sensor. Both procedures were in operation during the Arctic Airborne Stratospheric Expedition in 1989, and the Airborne Antarctic Ozone Experiment in 1987. Analysis of Arctic particles gathered in situ indicates the presence of nitric acid below a 'first appearance' temperature Tfa = 202 K. This is the same highest temperature at which PSCs are seen by the SAM II satellite. In comparison, a 'first appearance' temperature Tfa = 198 K as found for the Antarctic samples.
Pueschel, Rudolf F.↗
What does nitric acid really do to carbon nanofibers? [What nitric acid really does to carbon nanofibers]
Understanding the chemical nature of the surface of carbon nanofibers (CNF) is critical in assessing their fundamental properties and tailoring them for the right application. To gain such knowledge, we present here a detailed X-ray adsorption spectroscopy (XAS) study accompanied by high resolution transmission electron microscopy (TEM) micrographs of two morphologically different CNF pairs (tetrahedral amorphous carbon (ta-C) grown “open structured” fibers and traditional bamboo-like “closed structured” fibers), where the surface chemical properties and structural features of the fibers are investigated in depth and the effects of nitric acid treatment on the fibers are revealed. The morphology of the fiber and/or the original seed- and adhesion layers markedly affect the response of the fibers to the acid treatment. Results also show that the nitric acid treatment increases the observed sp 2 intensity and modifies the two types of fibers to become more-alike both structurally and with respect to their oxygen functionalities. Furthermore, the XAS and HRTEM results confirm that a short nitric acid treatment does not remove the Ni catalyst particle but, instead, oxidizes their surfaces, especially in the case of ta-C grown fibers.
36 MATERIALS SCIENCE↗
Degradation of CYANEX 301 in Contact with Nitric Acid Media
The nature of the degradation product obtained upon contacting CYANEX 301 (bis(2,4,4-trimethylpentyl)dithiophosphinic acid) with nitric acid has been elucidated and found to be a disulfide derivative. The first step to the degradation of CYANEX 301 in toluene has been studied using 31P{1H} NMR after being contacted with nitric acid media. The spectrum of the degradation product exhibits a complex multiplet around dP = 80 ppm. A succession of purifications of CYANEX 301 has resulted in single crystals of the acidic form and the corresponding ammonium salt. Unlike the original CYANEX 301, which consists of a complex diastereomeric mixture displaying all possible combinations of chiral orientations at the 2-methyl positions, the purified crystals were shown by single-crystal X-ray diffraction to be racemates, containing 50:50 mixtures of the [R;R] and [S;S] diastereomers. The comparison between the 31P {1H} NMR spectra of the degradation products resulting from the diastereomerically pure CYANEX 301 and the original diastereomeric mixture has elucidated the influence of the isomeric composition on the multiplicity of the 31P {1H} NMR peak. These NMR data indicate the initial degradation leads to a disulfide-bridged condensation product displaying multiple resonances due to phosphorus–phosphorus coupling, which is caused by the inequivalence of the two P atoms as a result of their different chirality. A total of nine different NMR resonances, six of which display phosphorus–phosphorus coupling, could be assigned, and the identity of the peaks corresponding to phosphorus atoms coupled to each other was confirmed by 31P {1H} homodecoupled NMR analysis.
99 GENERAL AND MISCELLANEOUS↗
Citric Acid Alternative to Nitric Acid Passivation
The Ground Systems Development and Operations GSDO) Program at NASA John F. Kennedy Space Center (KSC) has the primary objective of modernizing and transforming the launch and range complex at KSC to benefit current and future NASA programs along with other emerging users. Described as the launch support and infrastructure modernization program in the NASA Authorization Act of 2010, the GSDO Program will develop and implement shared infrastructure and process improvements to provide more flexible, affordable, and responsive capabilities to a multi-user community. In support of the GSDO Program, the purpose of this project is to demonstratevalidate citric acid as a passivation agent for stainless steel. Successful completion of this project will result in citric acid being qualified for use as an environmentally preferable alternative to nitric acid for passivation of stainless steel alloys in NASA and DoD applications.
Technology↗
Electrochemistry and Spectroelectrochemistry of the Pu (III/IV) and (IV/VI) Couples in Nitric Acid Systems
The solution chemistry of Pu in nitric acid is explored via electrochemistry and spectroelectrochemistry. By utilizing and comparing these techniques, an improved understanding of Pu behavior and its dependence on nitric acid concentration can be achieved. Here the Pu (III/IV) couple is characterized using cyclic voltammetry, square wave voltammetry, and a spectroelectrochemical Nernst step. Results indicate the formal reduction potential of the couple shifts negative with increasing acid concentration and reversible electrochemistry is no longer attainable above 6 M HNO3. Spectroelectrochemistry is also used to explore the irreversible oxidation of Pu(IV) to Pu(VI) and shine light on the mechanism and acid dependence of the redox reaction.
Lines, Amanda M.↗
Vapor pressures of concentrated nitric acid solutions in the composition range 83 to 97 percent nitric acid 0 to 6 percent nitrogen dioxide, 0 to 15 percent water, and in the temperature range 20 to 80 C
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Mckeown, A B↗
Diode laser spectrum of nitric acid at 5.9 microns and carbonyl sulfide frequency/wavelength standards for calibration of nitric acid bands both at 5.9 and 11.4 microns
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Wells, J. S.↗
Gamma Radiation-Induced Degradation of Acetohydroxamic Acid (AHA) in Aqueous Nitrate and Nitric Acid Solutions Evaluated by Multiscale Modelling
Acetohydroxamic acid (AHA) has been proposed for inclusion in advanced, single-cycle, used nuclear fuel reprocessing solvent systems for the reduction and complexation of plutonium and neptunium ions. For this application, a detailed description of the degradation of AHA in dilute aqueous nitric acid is required. To this end, we present a comprehensive, multiscale computer model for the coupled radiolytic and hydrolytic degradation of AHA in aqueous sodium nitrate and nitric acid solutions. Rate coefficients for the reactions of AHA and HA with the oxidizing nitrate radical were measured for the first time using pulsed electron radiolysis and used as inputs in the kinetic model. The computer model results are validated by comparison to experimental data from steady state gamma irradiations, for which the agreement is excellent. Here, the presented model accurately predicts the yields of the major degradation products of AHA: acetic acid, hydroxylamine, nitrous oxide, and molecular hydrogen.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
The role of nitric acid, kitty litter, and confinement in the 2014 WIPP accident
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Hobbs, Michael Lane [Sandia National Laboratories ↗
Laboratory studies of 2H evaporator scale dissolution in dilute nitric acid
The rate of 2H evaporator scale solids dissolution in dilute nitric acid has been experimentally evaluated under laboratory conditions in the SRNL shielded cells. The 2H scale sample used for the dissolution study came from the bottom of the evaporator cone section and the wall section of the evaporator cone. The accumulation rate of aluminum and silicon, assumed to be the two principal elemental constituents of the 2H evaporator scale aluminosilicate mineral, were monitored in solution. Aluminum and silicon concentration changes, with heating time at a constant oven temperature of 90 deg C, were used to ascertain the extent of dissolution of the 2H evaporator scale mineral. The 2H evaporator scale solids, assumed to be composed of mostly aluminosilicate mineral, readily dissolves in 1.5 and 1.25 M dilute nitric acid solutions yielding principal elemental components of aluminum and silicon in solution. The 2H scale dissolution rate constant, based on aluminum accumulation in 1.5 and 1.25 M dilute nitric acid solution are, respectively, 9.21E-04 ± 6.39E-04 min{sup -1} and 1.07E-03 ± 7.51E-05 min{sup -1}. Silicon accumulation rate in solution does track the aluminum accumulation profile during the first few minutes of scale dissolution. It however diverges towards the end of the scale dissolution. This divergence therefore means the aluminum-to-silicon ratio in the first phase of the scale dissolution (non-steady state conditions) is different from the ratio towards the end of the scale dissolution. Possible causes of this change in silicon accumulation in solution as the scale dissolution progresses may include silicon precipitation from solution or the 2H evaporator scale is a heterogeneous mixture of aluminosilicate minerals with several impurities. The average half-life for the decomposition of the 2H evaporator scale mineral in 1.5 M nitric acid is 12.5 hours, while the half-life for the decomposition of the 2H evaporator scale in 1.25 M nitric acid is 10.8 hours. Based on averaging the two half-lives from the 2H scale acid dissolution in 1.25 and 1.5 M nitric acid solutions, a reasonable half-live for the dissolution of 2H scales in dilute nitric acid is 11.7 ± 1.3 hours. The plant operational time for chemically cleaning (soaking) the 2H evaporator with dilute nitric acid is 32 hours. It therefore may require about 3 half-lives or less to completely dissolve most of the scales in the Evaporator pot which come into contact with the dilute nitric acid solution. On a mass basis, the Al-to-Si ratio for the scale dissolution in 1.5 M nitric acid averaged 1.30 ± 0.20 and averaged 1.18 ± 0.10 for the 2H scale dissolution in 1.25 M nitric acid. These aluminum-to-silicon ratios are in fairly good agreement with ratios from previous studies. Therefore, there is still more aluminum in the 2H evaporator scales than silicon which implies that there are no significant changes in scale properties which will exclude nitric acid as a viable protic solvent for aluminosilicate scale buildup dissolution from the 2H evaporator. Overall, the monitoring of the scale decomposition reaction in 1.25 and 1.5 M nitric acid may be better ascertained through the determination of aluminum concentration in solution than monitoring silicon in solution. Silicon solution chemistry may lead to partial precipitating of silicon with time as the scale and acid solution is heated.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Does Nitric Acid Dissociate at the Aqueous Solution Surface?
Nitric acid is a prevalent component of atmospheric aerosols, and the extent of nitric acid dissociation at aqueous interfaces is relevant to its role in heterogeneous atmospheric chemistry. Several experimental and theoretical studies have suggested that the extent of dissociation of nitric acid near aqueous interfaces is less than in bulk solution. Here, dissociation of HNO3 at the surface of aqueous nitric acid is quantified using X-ray photoelectron spectroscopy of the nitrogen local electronic structure. The relative amounts of undissociated HNO3(aq) and dissociated NO3-(aq) are identified by the distinguishable N1s core-level photoelectron spectra of the two species, and we determine the degree of dissociation, αint, in the interface (the first ~3 layers of solution) as a function of HNO3 concentration. Our measurements show that dissociation is decreased by approximately 20% near the solution interface compared with bulk, and furthermore that dissociation occurs even in the top-most solution layer. The experimental results are supported by first-principles MD simulations, which show that hydrogen-bonds between HNO3 and water molecules at the solution surface stabilize the molecular form at low concentration, in analogy to the stabilization of molecular HNO3 that occurs in bulk solution at high concentration. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.
54 ENVIRONMENTAL SCIENCES↗
Real refractive indices of infrared-characterized nitric-acid/ice films: Implications for optical measurements of polar stratospheric clouds
The infrared spectra of nitric-acid/ice films representative of polar stratospheric clouds (PSCs) were collected with simultaneous optical interference measurements to determine the real refractive indices at lambda = 632 nm. Ice and amphorous nitric-acid/ice films were prepared by condensation of water and nitric acid vapors onto a wedged Al2O3 substrate. The real refractive indices of these films were determined from the optical interference of a reflected helium-neon laser during film growth. The indices of the amphorous films varied smoothly from n = 1.30 for ice to n = 1.49 for nitric acid, similar to observations in previous work. We were unable to obtain the refractive index of crystlline films during adsorption because of optical scattering caused by surface roughness. Therefore crystlline nitric acid hydrate films were prepared by annealing amphorous nitric-acid/ice films. Further heating caused desorption of the crystalline hydrate films. During desorption, the refractive indices for ice, NAM (nitric acid monohydrate), alpha- and beta-NAT (nitric acid trihydrate) films were measured using the optical interference technique. In agreement with earlier data, the real refractive indices for ice and NAM determined in desorption were n = 1.30 +/- 0.01 and n = 1.53 +/- 0.03, respectively. The real refractive indices for alpha- and beta-NAT were found to be n = 1.51 +/- 0.01 and n greater than or equal to 1.46, respectively. Our measurements also suggest that the shape of crystalline nitric acid particles may depend on whether they nucleate from the liquid or by vapor deposition. If confirmed by future studies, this observation may provide a means of distinguishing the nucleation mechanism of crystalline PSCs.
Middlebrook, Ann M.↗
Modelling of the nitric acid reduction process: Application to materials behavior in reprocessing plants
In France, the recycling process of nuclear waste fuels involves the use of hot concentrated nitric acid. The understanding and the prediction of the structural materials (mainly austenitic stainless steels) behaviour requires the determination of the nitric acid reduction process. Nitric acid is indirectly reduced by an autocatalytic mechanism depending on the cathodic overpotential and the acid concentration. This mechanism has been widely studied. All the authors agree on its autocatalytic nature, characterized by the predominant role of the reduction products. It is also generally admitted that nitric acid or the nitrate ion are not the electro-active species. However, uncertainties remain concerning the nature of the electro-active species, the place where the catalytic species regenerates and the thermodynamic and kinetic behaviour of the reaction intermediates. The aim of this study is to clarify some of these uncertainties by performing an electrochemical investigation of the 4 mol.L -1 nitric acid reduction process at 40 deg. C occurring on an inert electrode (platinum or gold). An inert electrode was chosen as a working electrode in a first step in order to avoid its oxidation and focus the research on the reduction mechanism. This experimental work enabled to suggest a coherent sequence of electrochemical and chemical reactions. Then, a kinetic modelling of this sequence was carried out for a gold rotating disk system. In this objective, a thermodynamic study at 25 deg. C led to the evaluation of the composition of liquid and gaseous phases for nitric acid solutions from 0.5 to 22 mol.L -1. The kinetics of the reduction process of nitric acid 4 mol.L -1 was investigated by cyclic voltammetry and chrono-amperometry on an inert electrode at 40 deg. C. A coupling of chrono-amperometry and FTIR in gaseous phase led to the identification of the gaseous reduction products as a function of the cathodic overpotential. These different results showed that for potentials between 0.6 V/NHE and 1.15 V/NHE, the reduction process is autocatalytic. The regeneration of the electro-active species may take place at the surface of the electrode for lower over-potentials, and otherwise in solution. When the potential is lower than 0.6 V/ENH, the fast reduction of nitrogen oxide may lead to the rupture of the autocatalytic cycle. (authors)
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Safety Evaluation of Nitric Acid Reactions with Polysaccharides
The hazards of polysaccharides in a transuranic (TRU) waste drum exposed to nitric acid (HNO3) and metal nitrate salts have been evaluated, based on considerations of how complex nitrogen redox cycles carry out the aqueous phase oxidation of alcohols and related organic functional groups. Of particular emphasis is how these exothermic reactions, coupled with a positive feedback loop inherent to nitrogen redox chemistry, can initiate an autocatalytic thermal runaway and explosive gas generation. This poses the most significant hazard for a TRU waste drum under ambient conditions where acidic solution may be present, either in small quantities as free liquid or sorbed within a solid matrix. Regarding specific mechanistic details, nitric acid is an extremely potent oxidant but is remarkably inert, rarely interacting directly with oxidizable substrates, instead exerting its vast potential energy through lower oxidation state reactants such as nitrogen dioxide (NO 2 ) and nitrous acid (HNO 2 ). These lower oxidation states of nitrogen are generated from the slow self-decomposition of nitric acid, as a result of which oxidation reactions involving nitric acid that have not been preloaded with these reactants commonly experience a quiescent induction period. It is the end of this induction period when exothermic reactivity increases rapidly that the system is most vulnerable to autocatalytic thermal runaway. Metal nitrate salts promote this ambient temperature solution chemistry (cf. traditional oxidizer properties of metal nitrate salts, which operate in the solid state at elevated temperatures) by releasing nitric acid into the system. Although less reactive than alcohols by virtue of extensive hydrogen bonding, carbohydrates are oxidized by nitric acid through the same fundamental mechanisms, potentially proceeding through a series of oxidation steps. For polymeric carbohydrates (polysaccharides) the chemistry is complicated by a variety of competing side reactions, including acid-catalyzed hydrolytic depolymerization to more reactive (ultimately monomeric) units, as well as other degradation reactions promoted by radical mechanisms. For this reason, polysaccharides that are more susceptible to hydrolysis such as starches are more reactive than cellulose, with the attendant microbial population in starch based kitty litter adding a special aspect of reactivity. A spectrum of nitrogen containing gas products is generated from polysaccharide oxidation by nitric acid depending on the reaction conditions - for example, fuel lean mixtures tend towards producing more oxidized gases such as NO 2 , and thus favor an autocatalytic cycle, relative to fuel rich conditions that produce lower oxidation state gases such as nitrous oxide (N 2 O). These nitrogen based gases may be accompanied by variable quantities of carbon dioxide (CO 2 ), which may be generated from small molecule (e.g., oxalic acid) oxidation or from decarboxylation of previously oxidized functional groups.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗