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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Real-Time Automated pH Control within Batch Processes Relying on Raman pH Measurement

Nuclear fission is an energy source that can provide consistent power with very low associated carbon emissions. However, management of the used nuclear fuel is an important aspect of the application of nuclear power. Recycling of useful components from used fuel is an attractive option, but this involves chemical processing of the fuel. Possible chemical separation technologies that might be used in this regard are sensitive to solution pH. Raman spectroscopy is a promising technique for monitoring the pH of solutions in real time. Classical pH probes are too fragile to be used in the harsh environments encountered in nuclear fuel processing. Raman probes are robust and can withstand these harsh environments to track pH. Coupled with chemometric analysis, the demonstration of the use of Raman spectroscopy to track and predict the pH in carboxylate-buffered systems is made possible. Utilizing this spectroscopy in conjunction with Programmable Logic Controllers mimics industrial control systems used in many modern industrial settings. This showcases a pragmatic approach toward leveraging Raman spectroscopy and chemometric model outputs as inputs for a real-time control system. The model to predict pH created by chemometrics proved to be successful in tracking pH. The optimal pH for TALSPEAK extraction of lanthanides and actinides from aqueous solution is known to proceed in a narrow pH range of around pH = 2.8 ± 0.1. This study uses Raman optical monitoring and automated control to return and maintain solution pH within this range after acid or base perturbations move the solution pH well outside this region. Root-mean-square errors show that pH changes measured using Raman spectroscopy on the batch process solution are reliably measured and used to automatically correct and maintain solution pH. Measurement of solution pH tracks favorably with electrochemical pH probe comparison measurements. As a result, the ability to showcase Raman spectroscopy paired with chemometrics analysis acts as a durable, better alternative data source compared to traditional pH probes to optimize the separation efficiency in the used nuclear fuel processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Simulations of aerosol pH in China using WRF-Chem (v4.0): sensitivities of aerosol pH and its temporal variations during haze episodes

Aerosol pH is a fundamental property of aerosols in terms of atmospheric chemistry and its impact on air quality, climate, and health. Precise estimation of aerosol pH in chemical transport models (CTMs) is critical for aerosol modeling and thus influences policy development that partially relies on results from model simulations. We report the Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem) simulated PM 2.5 pH over China during a period with heavy haze episodes in Beijing, and explore the sensitivity of the modeled aerosol pH to factors including emissions of nonvolatile cations (NVCs) and NH 3 , aerosol phase state assumption, and heterogeneous production of sulfate. We find that default WRF-Chem could predict spatial patterns of PM 2.5 pH over China similar to other CTMs, but with generally lower pH values, largely due to the underestimation of alkaline species (NVCs and NH 3 ) and the difference in thermodynamic treatments between different models. Increasing NH 3 emissions in the model would improve the modeled pH in comparison with offline thermodynamic model calculations of pH constrained by observations. In addition, we find that the aerosol phase state assumption and heterogeneous sulfate production are important in aerosol pH predictions for regions with low relative humidity (RH) and high anthropogenic SO 2 emissions, respectively. These factors should be better constrained in model simulations of aerosol pH in the future. Analysis of the modeled temporal trend of PM 2.5 pH in Beijing over a haze episode reveals a clear decrease in pH from 5.2 ± 0.9 in a clean period to 3.6 ± 0.5 in a heavily polluted period. The increased acidity under more polluted conditions is largely due to the formation and accumulation of secondary species including sulfuric acid and nitric acid, even though being modified by alkaline species (NVCs, NH 3 ). Our result suggests that NO 2 oxidation is unlikely to be important for heterogeneous sulfate production during the Beijing haze as the effective pH for NO 2 oxidation of S(IV) is at a higher pH of ~6.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

General Kinetic Model for pH Dependence of Proton-Coupled Electron Transfer: Application to an Electrochemical Water Oxidation System

The pH dependence of proton-coupled electron transfer (PCET) reactions, which are critical to many chemical and biological processes, is a powerful probe for elucidating their fundamental mechanisms. Herein, a general, multichannel kinetic model is introduced to describe the pH dependence of both homogeneous and electrochemical PCET reactions. According to this model, a weak pH dependence can arise from the competition among multiple sequential and concerted PCET channels involving different forms of the redox species, such as protonated and deprotonated forms, as well as different proton donors and acceptors. The contribution of each channel is influenced by the relative populations of the reactant species, which often depend strongly on pH, leading to complex pH dependence of PCET apparent rate constants. This model is used to explain the origins of the experimentally observed weak pH dependence of the electrochemical PCET apparent rate constant for a ruthenium-based water oxidation catalyst attached to a tin-doped In2O3 (ITO) surface. The weak pH dependence is found to arise from the intrinsic differences in the rate constants of participating channels and the dependence of their relative contributions on pH. This model predicts that the apparent maximum rate constant will become pH-independent at higher pH, which is confirmed by experimental measurements. Our analysis also suggests that the dominant channels are electron transfer at lower pH and sequential PCET via electron transfer followed by fast proton transfer at higher pH. Furthermore, this work highlights the importance of considering multiple competing channels simultaneously for PCET processes.

Catalysts↗
DOE OSTI2021

Mechanistic Pathways for N 2 O Elimination from trans -R 3 Sn-O-N=N-O-SnR 3 and for Reversible Binding of CO 2 to R 3 Sn-O-SnR 3 (R = Ph, Cy)

The rate and mechanism of the elimination of N 2 O from trans-R 3 Sn-O-N=N-O-SnR 3 (R = Ph ( 1 Ph ) and R = Cy ( 1 Cy )) to form R 3 Sn-O-SnR 3 (R = Ph ( 2 Ph ) and R = Cy ( 2 Cy )) have been studied using both NMR and IR techniques to monitor the reactions in the temperature range of 39–79 °C in C 6 D 6 . Activation parameters for this reaction are ΔH ‡ = 15.8 ± 2.0 kcal·mol –1 and ΔS ‡ = –28.5 ± 5 cal·mol –1 ·K –1 for 1 Ph and ΔH ‡ = 22.7 ± 2.5 kcal·mol –1 and ΔS ‡ = –12.4 ± 6 cal·mol –1 ·K –1 for 1 Cy . Addition of O 2 , CO 2 , N 2 O, or PPh 3 to sealed tube NMR experiments did not alter in a detectable way the rate or product distribution of the reactions. Computational DFT studies of elimination of hyponitrite from trans-Me 3 Sn-O-N=N-O-SnMe 3 ( 1 Me ) yield a mechanism involving initial migration of the R 3 Sn group from O to N passing through a marginally stable intermediate product and subsequent N 2 O elimination. Reactions of 1 Ph with protic acids HX are rapid and lead to formation of R 3 SnX and trans-H 2 N 2 O 2 . Reaction of 1 Ph with the metal radical •Cr(CO) 3 C 5 Me 5 at low concentrations results in rapid evolution of N 2 O. At higher •Cr(CO) 3 C 5 Me 5 concentrations, evolution of CO 2 rather than N 2 O is observed. Addition of 1 atm or less CO 2 to benzene or toluene solutions of 2 Ph and 2 Cy resulted in very rapid reaction to form the corresponding carbonates R 3 Sn-O-C(=O)-O-SnR 3 (R = Ph ( 3 Ph ) and R = Cy ( 3 Cy )) at room temperature. Evacuation results in fast loss of bound CO 2 and regeneration of 2 Ph and 2 Cy . Variable temperature data for formation of 3 Cy yield ΔH o = –8.7 ± 0.6 kcal·mol –1 , ΔS o = –17.1 ± 2.0 cal·mol –1 ·K –1 , and ΔG o 298K = –3.6 ± 1.2 kcal·mol –1 . Furthermore, DFT studies were performed and provide additional insight into the energetics and mechanisms for the reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys

The potential-pH diagram, a graphical representation of the thermodynamically predominant reaction products in aqueous corrosion, is originally proposed for the corrosion of pure metals. The original approach only leads to stoichiometric oxides and hydroxides as the oxidation products. However, numerous experiments show that non-stoichiometric oxide scales are prevalent in the aqueous corrosion of alloys. In the present study, a room temperature potential-pH diagram considering oxide solid solutions, as a generalization of the traditional potential-pH diagram with stoichiometric oxides, is constructed for an FCC single-phase multi-principal element alloy (MPEA) based on the CALculation of PHAse Diagram method. The predominant reaction products, the ions in aqueous solution, and the cation distribution in oxides are predicted. The oxide solid solution is stabilized by the mixing free energy (or mixing entropy) and the stabilizing effect becomes more significant as the temperature increases. Consequently, solid solution oxides are stable in large regions of the potential-pH diagram and the mixing free energy mostly affects the equilibrium composition of the stable oxides, while the shape of stable regions for oxides is mostly determined by the structure of the stable oxides. Agreements are found for Ni 2+ , Fe 2+ , and Mn 2+ between the atomic emission spectroelectrochemistry measurements and thermodynamic calculations, while deviations exist for Cr 3+ and Co 2+ possibly due to surface complexation with species such as Cl - and the oxide dissolution. By incorporating the solution models of oxides, the current work presents a general and more accurate way to analyze the reaction products during aqueous corrosion of MPEAs.

Materials Science↗
NASA NTRS2002

Continuous pH monitoring in a perfused bioreactor system using an optical pH sensor

Monitoring and regulating the pH of the solution in a bioprocess is one of the key steps in the success of bioreactor operation. An in-line optical pH sensor, based on the optical absorption properties of phenol red present in the medium, was developed and tested in this work for use in NASA space bioreactors based on a rotating wall-perfused vessel system supporting a baby hamster kidney (BHK-21) cell culture. The sensor was tested over three 30-day and one 124-day cell runs. The pH sensor initially was calibrated and then used during the entire cell culture interval. The pH reported by the sensor was compared to that measured by a fiber optically coupled Shimadzu spectrophotometer and a blood gas analyzer. The maximum standard error of prediction for all the four cell runs for development pH sensor against BGA was +/-0.06 pH unit and for the fiber optically coupled Shimadzu spectrophotometer against the blood gas analyzer was +/-0.05 pH unit. The pH sensor system performed well without need of recalibration for 124 days. Copyright 2002 Wiley Periodicals, Inc.

Bioreactors↗
DOE OSTI2022

Method of evaluating pH using a metallic nanoparticle incorporated nanocomposite-based optical pH sensor

A method for evaluating the pH of an aqueous solution by utilizing the optical properties of a pH sensing material comprised of plurality of optically active nanoparticles dispersed in matrix material. The optically active nanoparticles have an electronic conductivity greater than about 10−1 S/cm and generally have an average nanoparticle diameter of less that about 500 nanometers, and the matrix material is a material which experiences a change in surface charge density over a pH range from 2.0 to 12.0 of at least 1%. The method comprises contacting the pH sensing material and the aqueous solution, illuminating the pH sensing material, and monitoring an optical signal generated through comparison of incident light and exiting light to determine the optical transmission, absorption, reflection, and/or scattering of the pH sensitive material. The optical signal of the pH sensitive material varies in response to the pH of the aqueous solution.

Ohodnicki, Jr., Paul R.↗
DOE OSTI2024

Mild pH-decoupling aqueous flow battery with practical pH recovery

Establishing a pH difference between the two electrolytes (pH decoupling) of an aqueous redox flow battery (ARFB) enables cell voltages exceeding the 1.23 V thermodynamic water-splitting window, but acid–base crossover penalizes efficiency and lifetime. Here we employ mildly acidic and mildly alkaline electrolytes to mitigate crossover, achieving high round-trip energy efficiency with open circuit voltage >1.7 V. We implemented an acid–base regeneration system to periodically restore electrolytes to their initial pH values. The combined system exhibited capacity fade rate <0.07% per day, round-trip energy efficiency >85% and approximately 99% Coulombic efficiency during stable operation for over a week. Cost analysis shows that the tolerance of acid–base crossover could be increased if the pH-decoupling ARFB achieved a higher voltage output and lower resistance. Finally, this work demonstrates principles for improving lifespan, rate capability and energy efficiency in high-voltage pH-decoupling ARFBs and pH recovery concepts applicable for pH-decoupling systems.

25 ENERGY STORAGE↗
NASA NTRS1995

17-4 PH and 15-5 PH

17-4 PH and 15-5 PH are extremely useful and versatile precipitation-hardening stainless steels. Armco 17-4 PH is well suited for the magnetic particle inspection requirements of Aerospace Material Specification. Armco 15-5 PH and 17-4 PH are produced in billet, plate, bar, and wire. Also, 15-5 PH is able to meet the stringent mechanical properties required in the aerospace and nuclear industries. Both products are easy to heat treat and machine, making them very useful in many applications.

Johnson, Howard T.↗
DOE OSTI2020

Seawater pH reconstruction using boron isotopes in multiple planktonic foraminifera species with different depth habitats and their potential to constrain pH and <i>p</i>CO<sub>2</sub> gradients

Boron isotope systematics of planktonic foraminifera from core-top sediments and culture experiments have been studied to investigate the sensitivity ofδ11B of calcite tests to seawater pH. However, our knowledge of the relationship between δ11B and pH remains incomplete for many taxa. Thus, to expand the potential scope of application of this proxy, we report δ11B data for seven different species of planktonic foraminifera from sediment core tops. We utilize a method for the measurement of small samples of foraminifera and calculate the δ11B-calcite sensitivity to pH for Globigerinoides ruber, Trilobus sacculifer (sacc or without sacc), Orbulina universa, Pulleniatina obliquiloculata, Neogloboquadrina dutertrei, Globorotalia menardii, and Globorotalia tumida, including for unstudied core tops and species. These taxa have diverse ecological preferences and are from sites that span a range of oceanographic regimes, including some that are in regions of air–sea equilibrium and others that are out of equilibrium with the atmosphere. The sensitivity of δ11Bcarbonate to δ11Bborate (e.g., Δδ11Bcarbonate/Δδ11Bborate) in core tops is consistent with previous studies for T. sacculifer and G. ruber and close to unity for N. dutertrei, O. universa, and combined deep-dwelling species. Deep-dwelling species closely follow the core-top calibration fo rO. universa, which is attributed to respiration-driven microenvironments likely caused by light limitation and/or symbiont–host interactions. Our data support the premise that utilizing boron isotope measurements of multiple species within a sediment core can be utilized to constrain vertical profiles of pH andpCO2 at sites spanning different oceanic regimes, thereby constraining changes in vertical pH gradients and yielding insights into the past behavior of the oceanic carbon pumps.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

pH Homeostasis and Sodium Ion Pumping by Multiple Resistance and pH Antiporters in Pyrococcus furiosus

Multiple Resistance and pH (Mrp) antiporters are seven-subunit complexes that couple transport of ions across the membrane in response to a proton motive force (PMF) and have various physiological roles, including sodium ion sensing and pH homeostasis. The hyperthermophilic archaeon Pyrococcus furiosus contains three copies of Mrp encoding genes in its genome. Two are found as integral components of two respiratory complexes, membrane bound hydrogenase (MBH) and the membrane bound sulfane sulfur reductase (MBS) that couple redox activity to sodium translocation, while the third copy is a stand-alone Mrp. Sequence alignments show that this Mrp does not contain an energy-input (PMF) module but contains all other predicted functional Mrp domains. The P. furiosus Mrp deletion strain exhibits no significant changes in optimal pH or sodium ion concentration for growth but is more sensitive to medium acidification during growth. Cell suspension hydrogen gas production assays using the deletion strain show that this Mrp uses sodium as the coupling ion. Mrp likely maintains cytoplasmic pH by exchanging protons inside the cell for extracellular sodium ions. Deletion of the MBH sodium-translocating module demonstrates that hydrogen gas production is uncoupled from ion pumping and provides insights into the evolution of this Mrp-containing respiratory complex.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1986

Computer simulation of immobilized pH gradients at acidic and alkaline extremes - A quest for extended pH intervals

Computer simulations of the concentration profiles of simple biprotic ampholytes with Delta pKs 1, 2, and 3, on immobilized pH gradients (IPG) at extreme pH values (pH 3-4 and pH 10-11) show markedly skewed steady-state profiles with increasing kurtosis at higher Delta pK values. Across neutrality, all the peaks are symmetric irrespective of their Delta pK values, but they show very high contribution to the conductivity of the background gel and significant alteration of the local buffering capacity. The problems of skewness, due to the exponential conductivity profiles at low and high pHs, and of gel burning due to a strong electroosmotic flow generated by the net charges in the gel matrix, also at low and high pHs, are solved by incorporating in the IPG gel a strong viscosity gradient. This is generated by a gradient of linear polyacrylamide which is trapped in the gel by the polymerization process.

Mosher, Richard A.↗
DOE OSTI2020

Fate of arsenic during up to 4.5 years of aging of Fe III -As V coprecipitates at acidic pH: Effect of reaction media (Nitrate vs. Sulfate), Fe/As molar ratio, and pH

Iron-arsenate (Fe III -As V ) coprecipitate generated in acid mine drainage and hydrometallurgical practices is one of the potential sources of As contamination in the environment. However, the As behavior as well as the transformation process of the Fe III -As V coprecipitate is still not fully understood under acidic conditions. This work systematically studied the effect of reaction media (sulfate vs. nitrate), Fe/As molar ratios, and acidic pH values on the transformation rates, routes, and products of the Fe III -As V coprecipitates at different temperatures during up to 4.5 years of aging. X-ray diffraction (XRD), transmission electron spectroscopy (TEM), Raman spectroscopy, and extended X-ray absorption fine structure spectroscopy (EXAFS) results showed that the Fe III -As V coprecipitates with Fe/As = 2 transformed to scorodite at pH 4 in both sulfate and nitrate media with poorly crystalline ferric arsenate as precursor. In comparison, for the Fe/As = 4 samples, parascorodite and hematite were formed in sulfate and nitrate media, respectively. We note arsenic was released into the liquid phase during the aging process for the samples with Fe/As = 2 and 4. The aqueous As concentrations ([As] aq ) in sulfate media were larger than those in nitrate media for both the Fe/As = 2 and 4 samples. In addition, the transformation products were goethite and Na-jarosite at Fe/As = 8 and 16, pH 2.5 with the decrease of [As] aq . The results also indicated that 6-line ferrihydrite was a common intermediate for many Fe-As transformation processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cluster defects in gibbsite nanoplates grown at acidic to neutral pH

Gibbsite [α-Al(OH) 3 ] is the solubility limiting phase for aluminum across a wide pH range, and it is a common mineral phase with many industrial applications. The growth mechanism of this layered-structure material, however, remains incompletely understood. Synthesis of gibbsite at low to circumneutral pH yields nanoplates with substantial interlayer disorder. Here we examine defects in this material in detail, and the effects of recrystallization in highly alkaline sodium hydroxide solution at 80 °C. We employed a multimodal approach, including scanning electron microscopy, magic-angle spinning nuclear magnetic resonance (MAS-NMR), Raman and infrared spectroscopies, X-ray diffraction (XRD), and X-ray total scattering pair distribution function (XPDF) analysis to characterize the ageing of the nanoplates over several days. Additionally, XRD and XPDF indicate that gibbsite nanoplates precipitated at circumneutral pH contain dense, truncated sheets imparting a local difference in interlayer distance. These interlayer defects appear well described by flat Al 13 aluminum hydroxide nanoclusters nearly isostructural with gibbsite sheets present under synthesis conditions and trapped as interlayer inclusions during growth. Ageing at elevated temperature in alkaline solutions gradually improves crystallinity, showing a gradual increase in H-bonding between interlayer OH groups. Between 7 to 8 vol% of the initial gibbsite nanoparticles exhibit this defect, with the majority of differences disappearing after 2–4 hours of recrystallization in alkaline solution. The results not only identify the source of disorder in gibbsite formed under acidic/neutral conditions but also point to a possible cluster-mediated growth mechanism evident through inclusion of relict oligomers with gibbsite-like topology trapped in the interlayer spaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗