Cations impact radical reaction dynamics in concentrated multicomponent aqueous solutions.

Ultraviolet (UV) photolysis of nitrite ions (NO2-) in aqueous solutions produces a suite of radicals, viz., NO·, O-, ·OH, and ·NO2. The O- and NO· radicals are initially formed from the dissociation of photoexcited NO2-. The O- radical undergoes reversible proton transfer with water to generate ·OH. Both ·OH and O- oxidize the NO2- to ·NO2 radicals. The reactions of ·OH occur at solution diffusion limits, which are influenced by the nature of the dissolved cations and anions. Here, we systematically varied the alkali metal cation, spanning the range from strongly to weakly hydrating ions, and measured the production of NO·, ·OH, and ·NO2 radicals during UV photolysis of alkaline nitrite solutions using electron paramagnetic resonance spectroscopy with nitromethane spin trapping. Comparing the data for the different alkali cations revealed that the nature of the cation had a significant effect on production of all three radical species. Radical production was inhibited in solutions with high charge density cations, e.g., lithium, and promoted in solutions containing low charge density cations, e.g., cesium. Through complementary investigations with multinuclear single pulse direct excitation nuclear magnetic resonance (NMR) spectroscopy and pulsed field gradient NMR diffusometry, cation-controlled solution structures and extent of NO2- solvation were determined to alter the initial yields of ·NO and ·OH radicals as well as alter the reactivity of NO2- toward ·OH, impacting the production of ·NO2. The implications of these results for the retrieval and processing of low-water, highly alkaline solutions that comprise legacy radioactive waste are discussed.

Correction: Solubilities in aqueous nitrate solutions that appear to reverse the law of mass action.

Correction for 'Solubilities in aqueous nitrate solutions that appear to reverse the law of mass action' by Jacob G. Reynolds et al., Phys. Chem. Chem. Phys., 2021, 23, 21407-21418, DOI: 10.1039/D1CP03124D.

Solubilities in aqueous nitrate solutions that appear to reverse the law of mass action.

Non-ideal aqueous electrolyte solutions have been studied since the start of the application of thermodynamics to chemistry in the late 19th century. The present study examines some of the most extreme non-ideal behavior ever observed: solubilities of alkali and NH4+ nitrate salts in water that appear to behave the opposite of how the Law of Mass Action would predict. A literature review discovered that the solubilities of NH4NO3 and many alkali nitrate salts increases when another nitrate-bearing electrolyte is added to solution. These occurrences were in concentrated solutions with insufficient water to provide all ions their preferred hydration number without sharing waters between ions. This water deficit results in the formation of contact ion-pairs as well as larger ion-clusters. These ion-clusters may be favored when there is more than one type of monovalent cation present.

Hydroxide promotes ion pairing in the NaNO2-NaOH-H2O system.

Nitrite (NO2-) is a prevalent nitrogen oxyanion in environmental and industrial processes, but its behavior in solution, including ion pair formation, is complex. This solution phase complexity impacts industries such as nuclear waste treatment, where NO2- significantly affects the solubility of other constituents present in sodium hydroxide (NaOH)-rich nuclear waste. This work provides molecular scale information into sodium nitrite (NaNO2) and NaOH ion-pairing processes to provide a physical basis for later development of thermodynamic models. Solubility isotherms of NaNO2 in aqueous mixtures with NaOH and total alkalinity were also measured. Spectroscopic characterization of these solutions utilized high-field nuclear magnetic resonance spectroscopy (NMR) and Raman spectroscopy, with additional solution structure detailed by X-ray total scattering pairwise distribution function analysis (X-ray PDF). Despite the NO2- deformation Raman band's insensitivity to added NaOH in saturated NaNO2 solutions, 23Na and 15N NMR studies indicated the Na+ and NO2- chemical environments change likely due to ion pairing. The ion pairing correlates with a decrease in diffusion coefficient of solution species as measured by pulsed field gradient 23Na and 1H NMR. Two-dimensional correlation analyses of the 2800-4000 cm-1 Raman region and X-ray PDF indicated that saturated NaNO2 and NaOH mixtures disrupt the hydrogen network of water into a new structure where the length of the OO correlations is contracted relative to the typical H2O structure. Beyond describing the solubility of NaNO2 in a multicomponent electrolyte mixture, these results also indicate that nitrite exhibits greater ion pairing in mixtures of concentrated NaNO2 and NaOH than in comparable solutions with only NaNO2.

Influence of soluble oligomeric aluminum on precipitation in the Al-KOH-H2O system.

The role of oligomeric aluminate species in the precipitation of aluminum (Al) phases such as gibbsite (α-Al(OH)3) from aqueous hydroxide solutions remains unclear and difficult to probe directly, despite its importance for developing accurate predictions of Al solubility in highly alkaline systems. Precipitation in this system entails a transition from predominantly tetrahedrally coordinated aluminate (Al(OH)4-) species in solution to octahedrally coordinated Al in gibbsite. Here we report a quantitative study of dissolved Al in the Al-KOH-H2O system using a combination of molecular spectroscopies. We establish a relationship between changes in 27Al NMR chemical shifts and the relative intensity of Raman vibrational bands, indicative of variations in the ensemble speciation of Al in solution, and the formation of unique contact ion pair interactions with the aluminate dimer, Al2O(OH)62-. A strong correlation between the extent of Al oligomerization and the amount of solvated Al was demonstrated by systematically varying the KOH : Al molar ratio. The concentration of dissolved oligomeric Al in solution also directly impacted the particle size and morphology of the precipitated gibbsite. High concentrations of dimeric Al2O(OH)62- yielded smaller and more numerous anhedral to subhedral gibbsite particles, while low concentrations yielded fewer and larger euhedral gibbsite platelets. The collective observations suggest a key role for the Al2O(OH)62- dimer in promoting gibbsite precipitation from solution, with the potassium ion-paired dimer catalyzing a more rapid transformation of Al from tetrahedral coordination in solution to octahedral coordination in gibbsite.

Ion-ion interactions enhance aluminum solubility in alkaline suspensions of nano-gibbsite (α-Al(OH)3) with sodium nitrite/nitrate.

Despite widespread industrial importance, predicting metal solubilities in highly concentrated, multicomponent aqueous solutions is difficult due to poorly understood ion-ion and ion-solvent interactions. Aluminum hydroxide solid phase solubility in concentrated sodium hydroxide (NaOH) solutions is one such case, with major implications for ore refining, as well as processing of radioactive waste stored at U.S. Department of Energy legacy sites, such as the Hanford Site, Washington State. The solubility of gibbsite (α-Al(OH)3) is often not well predicted because other ions affect the activity of hydroxide (OH-) and aluminate (Al(OH)4-) anions. In the present study, we systematically examined the influence of key anions, nitrite (NO2-) and nitrate (NO3-), as sodium salts on the solubility of α-Al(OH)3 in NaOH solutions taking care to establish equilibrium from both under- and oversaturation. Rapid equilibration was enabled by use of a highly pure and crystalline synthetic nano-gibbsite of well-defined particle size and shape. Measured dissolved aluminum concentrations were compared with those predicted by an α-Al(OH)3 solubility model derived for simple Al(OH)4-/OH- systems. Specific anion effects were expressed as an enhancement factor (Alenhc) conveying the excess of dissolved aluminum. At 45 °C, NaNO2 and NaNO3-containing systems exhibited Alenhc values of 2.70 and 1.88, respectively, indicating significant enhancement. The solutions were examined by Raman and high-field 27Al NMR spectroscopy, indicating specific interactions including Al(OH)4--Na+ contact ion pairing and Al(OH)4--NO2-/NO3- ion-ion interactions. Dynamic evolution of the α-Al(OH)3 particles including growth and agglomeration was observed revealing the importance of dissolution/reprecipitation in establishing equilibrium. These studies indicate that incomplete ion hydration, as a result of the low water activity in these concentrated electrolytes, results in: (i) enhanced reactivity of the hydroxide ion with respect to α-Al(OH)3; (ii) increased concentrations of Al(OH)4- in solution; and (iii) stronger ion-ion interactions that act to stabilize the supersaturated solutions. This information on the mechanisms by which α-Al(OH)3 becomes supersaturated is essential for more energy-efficient aluminum processing technologies, including the treatment of millions of gallons of Al(OH)4--rich high-level radioactive waste.

Multinuclear PFGSTE NMR description of 39K, 23Na, 7Li, and 1H specific activation energies governing diffusion in alkali nitrite solutions.

While pulsed field gradient stimulated echo nuclear magnetic resonance (PFGSTE NMR) spectroscopy has found widespread use in the quantification of self-diffusivity for many NMR-active nuclei, extending this technique to uncommon nuclei with unfavorable NMR properties remains an active area of research. Potassium-39 (39K) is an archetypical NMR nucleus exhibiting an unfavorable gyromagnetic ratio combined with a very low Larmor frequency. Despite these unfavorable properties, this work demonstrates that 39K PFGSTE NMR experiments are possible in aqueous solutions of concentrated potassium nitrite. Analysis of the results indicates that 39K NMR diffusometry is feasible when the nuclei exhibit spin-lattice and spin-spin relaxation coefficients on the order of 60-100 ms and 50-100 ms, respectively. The diffusivity of 39K followed Arrhenius behavior, and comparative 23Na, 7Li, and 1H PFGSTE NMR studies of equimolal sodium nitrite and lithium nitrite solutions led to correlations between the enthalpy of hydration with the activation energy governing self-diffusion of the cations and also of water. Realizing the feasibility of 39K PFGSTE NMR spectroscopy has a widespread impact across energy sciences because potassium is a common alkali element in energy storage materials and other applications.

Resolving intermediates during the growth of aluminum deuteroxide (Hydroxide) polymorphs in high chemical potential solutions.

Aluminum hydroxide polymorphs are of widespread importance yet their kinetics of nucleation and growth remain beyond the reach of current models. Here we attempt to unveil the reaction processes underlying the polymorphs formation at high chemical potential. We examine their formation in-situ from supersaturated alkaline sodium aluminate solutions using deuteration and time-resolved neutron pair distribution function analyses, which indicate the formation of individual Al(OD)3 layers as an intermediate particle phase. These layers ultimately stack to form gibbsite- or bayerite-like layered heterostructures. Ex-situ characterization of the recovered precipitates using 27Al magic angle spinning nuclear magnetic resonance spectroscopy, Raman, X-ray diffraction, and scanning electron microscopy, suggests the presence of additional intermediate states, an amorphous compound bearing both tetrahededrally- and penta-coordinated Al3+. These observations reveal the complex pathways to form Al(OD)3 monolayers via either transient pentacoordinate species or amorphous-to-ordered transitions. The subsequent crystallization of admixed gibbsite/bayerite is followed by an Al(OD)3 monolayer attachment process.

The apparent solubility of aluminum (III) in Hanford high-level waste.

The solubility of aluminum in Hanford nuclear waste impacts on the processability of the waste by a number of proposed treatment options. For many years, Hanford staff has anecdotally noted that aluminum appears to be considerably more soluble in Hanford waste than the simpler electrolyte solutions used as analogues. There has been minimal scientific study to confirm these anecdotal observations, however. The present study determines the apparent solubility product for gibbsite in 50 tank samples. The ratio of hydroxide to aluminum in the liquid phase for the samples is calculated and plotted as a function of total sodium molarity. Total sodium molarity is used as a surrogate for ionic strength, because the relative ratios of mono-, di- and trivalent anions are not available for all of the samples. These results were compared to the simple NaOH-NaAl(OH)(4)-H(2)O system, and the NaOH-NaAl(OH)(4)-NaCl-H(2)O system data retrieved from the literature. The results show that gibbsite is apparently more soluble in the samples than in the simple systems whenever the sodium molarity is greater than 2M. This apparent enhanced solubility cannot be explained solely by differences in ionic strength. The change in solubility with ionic strength in simple systems is small compared to the difference between aluminum solubility in Hanford waste and the simple systems. The reason for the apparent enhanced solubility is unknown, but could include kinetic or thermodynamic factors that are not present in the simple electrolyte systems. Any kinetic explanation would have to explain why the samples are always supersaturated whenever the sodium molarity is above 2M. Real waste characterization data should not be used to validate thermodynamic solubility models until it can be confirmed that the apparent enhanced gibbsite solubility is a thermodynamic effect and not a kinetic effect.

The controlling role of atmosphere in dawsonite versus gibbsite precipitation from tetrahedral aluminate species.

In highly alkaline solution, aluminum speciates as the tetrahedrally coordinated aluminate monomer, Al(OH)4- and/or dimer Al2O(OH)62-, yet precipitates as octahedrally coordinated gibbsite (Al(OH)3). This tetrahedral to octahedral transformation governs Al precipitation, which is crucial to worldwide aluminum (Al) production, and to the retrieval and processing of Al-containing caustic high-level radioactive wastes. Despite its significance, the transformation pathway remains unknown. Here we explore the roles of atmospheric water and carbon dioxide in mediating the transformation of the tetrahedrally coordinated potassium aluminate dimer salt (K2Al2O(OH)6) to gibbsite versus potassium dawsonite (KAl(CO3)(OH)2). A combination of in situ attenuated total reflection infrared spectroscopy, ex situ micro X-ray diffraction, and multivariate curve resolution-alternating least squares chemometrics analysis reveals that humidity plays a key role in the transformation by limiting the amount of alkalinity neutralization by dissolved CO2. Lower humidity favors higher alkalinity and incorporation of carbonate species in the final Al product to form KAl(CO3)(OH)2. Higher humidity enables more acid generation that destabilizes dawsonite and favors gibbsite as the solubility limiting phase. This indicates that the transition from tetra- to octahedrally coordinated Al does not have to occur in bulk solution, as has often been hypothesized, but may instead occur in thin water films present on mineral surfaces in humid environments. Our findings suggest that phase selection can be controlled by humidity, which could enable new pathways to Al transformations useful to the Al processing industry, as well as improved understanding of phases that appear in caustic Al-bearing solutions exposed to atmospheric conditions.

Large cemented gibbsite agglomerates in alkaline nuclear waste at the Hanford site and the impacts to remediation.

Recent work with the remediation of legacy alkaline nuclear waste has focused on nanometer and micrometer particle sizes, emphasizing how these small particles can impact efforts to treat the waste. Building upon this work, we present here findings that show very large particles (several centimeters in size) also exist in these waste which likewise play an important role in the remediation process. While large cemented gibbsite nodules have been periodically reported in acid soils in the literature, this study found similar large gibbsite agglomerates (7 cm in diameter) in alkaline nuclear waste, the first time that such large agglomerates have been identified in an alkaline environment. The morphology of the gibbsite in the agglomerates that were grown over more than 40 years of storage in the waste tank were similar to the much smaller agglomerates that have been reported in previous shorter term studies. Fluid dynamics calculations indicate that these cemented particles would be difficult to mobilize with standard jet slurry technologies, which is consistent with their persistence in the waste heel after jet sluicing of the tank.

Salt Solubilities in Aqueous Solutions of NaNO3, NaNO2, NaCl, and NaOH: A Hofmeister-like Series for Understanding Alkaline Nuclear Waste.

Nonelectrolyte solubility in electrolyte solutions follow the Hofmeister series, but the applicability of the series to salt solubility has been less appreciated. This study, using solubility data for thirteen sodium-bearing salts, shows that salts are consistently salted out by electrolytes important to alkaline nuclear waste in the order NaOH > NaCl > NaNO2 > NaNO3 at 298.15 K, which is the same order as the Hofmeister series. Graphical presentation allowed for easy separation of the common ion effect (caused by the addition of Na+) from the salting-out effect (caused by the presence of anions) because there is a large difference between the solubility of a given salt in different background electrolytes at a common Na+ molality. The trend persists even in very high electrolyte concentrations where essentially all of the water molecules must be in the coordination sphere of an ion, which means that the effect of electrolytes on "bulk water" is not the cause of the trend. These specific interactions more likely result from the sharing of water molecules between ions, augmented by differences in ion-pairing of the electrolytes. The Hofmeister series has practical application to the management of alkaline high-level radioactive waste created at nuclear fuel reprocessing facilities, where a predictive understanding of salt solubility is essential for blending wastes of disparate compositions prior to treatment.

Development of a carbonate crust on alkaline nuclear waste sludge at the Hanford site.

Hard crusts on aging plutonium production waste have hindered the remediation of the Hanford Site in southeastern Washington, USA. In this study, samples were analyzed to determine the cause of a hard crust that developed on the highly radioactive sludge during 20 years of inactivity in one of the underground tanks (tank 241-C-105). Samples recently taken from the crust were compared with those acquired before the crust appeared. X-ray diffraction and scanning electron microscopy (SEM) indicated that aluminum and uranium phases at the surface had converted from (hydr)oxides (gibbsite and clarkeite) into carbonates (dawsonite and cejkaite) and identified trona as the cementing phase, a bicarbonate that formed at the expense of thermonatrite. Since trona is more stable at lower pH values than thermonatrite, the pH of the surface decreased over time, suggesting that CO2 from the atmosphere lowered the pH. Thus, a likely cause of crust formation was the absorption of CO2 from the air, leading to a reduction of the pH and carbonation of the waste surface. The results presented here help establish a model for how nuclear process waste can age and can be used to aid future remediation and retrieval activities.

Ab Initio Molecular Dynamics Reveal Spectroscopic Siblings and Ion Pairing as New Challenges for Elucidating Prenucleation Aluminum Speciation.

The characterization of prenucleation species is essential to understand crystallization mechanisms across many chemical systems and often involves the use of vibrational spectroscopy. Nowhere is this more evident than in the development of "green" aluminum processing technologies, where detailed understanding of the speciation of aluminum and its polynuclear analogues in highly alkaline, low water solutions is elusive. The aluminate anion Al(OH)4- predominates in alkaline conditions, yet equilibrium with dimeric species, either µ-oxo Al2O(OH)62- or di-µ-hydroxo Al2(OH)82-, can be assumed. Using ab initio molecular dynamics with full solvation and the presence of counterions, this work reconciles previous contradictory studies that had concluded only a single species under relevant solution conditions. We reveal that the two dimers are energetically separated by 2 kcal/mol in pure water but that the stability of each can be reversed by ion pairing expected in saturated salt solutions. Simulated Raman and IR spectra for each species (accounting for anharmonicity and the fluctuating solvating environment) provide the first proof that the considered species are "spectroscopic siblings", whose multiple overlapping bands prevent definitive assertions in terms of speciation when compared to the experimental spectra. These observations are likely to hold in higher order aluminate oligomers and as such present a massive challenge toward understanding the crystallization mechanisms relevant to aluminum processing.

Solid-phase zirconium and fluoride species in alkaline zircaloy cladding waste at Hanford.

The United States Department of Energy Hanford Site, near Richland, Washington, USA, processed plutonium between 1944 and 1987. Fifty-six million gallons of waste of various origins remain, including waste from removing zircaloy fuel cladding using the so-called Zirflex process. The speciation of zirconium and fluoride in this waste is important because of the corrosivity and reactivity of fluoride as well as the (potentially) high density of Zr-phases. This study evaluates the solid-phase speciation of zirconium and fluoride using X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). Two waste samples were analyzed: one waste sample that is relatively pure zirconium cladding waste from tank 241-AW-105 and another that is a blend of zirconium cladding wastes and other high-level wastes from tank 241-C-104. Villiaumite (NaF) was found to be the dominant fluoride species in the cladding waste and natrophosphate (Na7F[PO4]2 · 19H2O) was the dominant species in the blended waste. Most zirconium was present as a sub-micron amorphous Na-Zr-O phase in the cladding waste and a Na-Al-Zr-O phase in the blended waste. Some zirconium was present in both tanks as either rounded or elongated crystalline needles of Na-bearing ZrO2 that are up to 200 µm in length. These results provide waste process planners the speciation data needed to develop disposal processes for this waste.

Evidence for dawsonite in Hanford high-level nuclear waste tanks.

Gibbsite [Al(OH)(3)] and boehmite (AlOOH) have long been assumed to be the most prevalent aluminum-bearing minerals in Hanford high-level nuclear waste sludge. The present study shows that dawsonite [NaAl(OH)(2)CO(3)] is also a common aluminum-bearing phase in tanks containing high total inorganic carbon (TIC) concentrations and (relatively) low dissolved free hydroxide concentrations. Tank samples were probed for dawsonite by X-ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive Spectrometry (SEM-EDS) and Polarized Light Optical Microscopy. Dawsonite was conclusively identified in four of six tanks studied. In a fifth tank (AN-102), the dawsonite identification was less conclusive because it was only observed as a Na-Al bearing phase with SEM-EDS. Four of the five tank samples with dawsonite also had solid phase Na(2)CO(3) · H(2)O. The one tank without observable dawsonite (Tank C-103) had the lowest TIC content of any of the six tanks. The amount of TIC in Tank C-103 was insufficient to convert most of the aluminum to dawsonite (Al:TIC mol ratio of 20:1). The rest of the tank samples had much lower Al:TIC ratios (between 2:1 and 0.5:1) than Tank C-103. One tank (AZ-102) initially had dawsonite, but dawsonite was not observed in samples taken 15 months after NaOH was added to the tank surface. When NaOH was added to a laboratory sample of waste from Tank AZ-102, the ratio of aluminum to TIC in solution was consistent with the dissolution of dawsonite. The presence of dawsonite in these tanks is of significance because of the large amount of OH(-) consumed by dawsonite dissolution, an effect confirmed with AZ-102 samples.