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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,351 records · Page 75
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Variable hydrazine coordination modes from reactions with dichlorotris(triphenylphosphine)ruthenium(II)

The reactivity of the prominent ruthenium(II) catalyst and precursor, RuCl 2 (PPh 3 ) 3 , was explored with hydrazine and its derivatives. The reactions produced 6-coordinate ruthenium(II) products that bond with the hydrazine moiety in bridging (NH 2 NH 2 or NH 2 NHMe), end-on (NH 2 NHMe, NH 2 NHPh, or NH 2 NMe 2 ), or side-on (NH 2 NMe 2 ) fashions. The products have been characterized by single crystal X-ray diffraction and 31 P NMR spectroscopy. With NH 2 NH 2 , the dimeric product, [RuCl 2 (PPh 3 ) 2 ] 2 ($μ$-N 2 H 4 ) 2 , was formed under all conditions used. For other hydrazines, the reaction stoichiometry governed product formation to yield either bimetallic or monomeric products. When the RuCl 2 (PPh 3 ) 3 to hydrazine derivative ratio was 1:1 or lower, bimetallic complexes were formed while a 1:2 ratio produced monomeric compounds. The exception to the latter occurs with the production of the monomeric compound, RuCl 2 (PPh 3 ) 2 ($η$ 2 -NH 2 NMe 2 ), that forms employing a 1:1 ratio. In addition to stoichiometry, steric factors and hydrogen bonding played a significant role in dictating the bonding mode of hydrazines. The bimetallic complexes were further reacted to yield the corresponding monomeric products, adopting the form RuCl 2 (PPh 3 ) 2 (L) 2 (L = NH 2 NHMe, NH 2 NHPh, or NH 2 NMe 2 ). Reactions utilizing less than a 1:2 ratio of RuCl 2 (PPh 3 ) 3 to NH 2 NMe 2 produced a mixture of products that appear to be in equilibrium. In conclusion, FT calculations were performed to gain insight into the reaction energetics and molecular stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A series of four-coordinate heteroleptic copper(I) complexes with diimine and β-diketiminate ligands

In this paper, a series of heteroleptic bis-chelate copper(I) complexes of the general formula Cu(N^N)(NacNac R ), where N^N is the diimine ligand and NacNac R is the β-diketiminate ligand are introduced. The complexes are easily prepared by reacting NacNac ligands with CuO t Bu in the presence of diimine ligands. The molecular structures of all complexes are characterized by NMR spectroscopy and X-ray crystallography. The studies of cyclic voltammetry and UV–vis absorption spectra show that the HOMO and the LUMO energy level can be tailored by changing the substitution pattern of each ligand. The oxidation potential is dependent on the NacNac ligand, and the reduction potential shows the dependence on the diimine ligand. In conclusion, tunable redox potentials and a wide range of visible absorption can make these copper(I) complexes promising candidates for applications in solar light harvesting.

14 SOLAR ENERGY↗
DOE OSTI2023

Synthesis and structure of Americium(III) diglycolate oxalate Trihydrate, Am(ODA)(C 2 O 4 )(H 2 O) 3

Improving f-element separations is important for actinide(III) (An 3+ ) and lanthanide(III) (Ln 3+ ) based technologies. Unfortunately, An 3+ and Ln 3+ ions are difficult to separate from one another because they have similar chemical characteristics. One successful separation method utilizes anion exchange chromatography. This approach exploits differences in An 3+ and Ln 3+ Lewis acidities and their varying abilities to attract anionic complexing agents, like oxalates (C 2 O 4 2– ) and diglycolates (ODA 2– ). The resulting negatively charged complexes are then separated using an anion exchange resin. To better understand how this anion exchange separation works, we reacted Am 3+ (aq) (aq designates Am 3+ dissolved in water) with the anion exchange complexing agents (H 2 C 2 O 4 and H 2 ODA). Here, the resulting Am(ODA)(C 2 O 4 )(H 2 O) 3 product was characterized using single crystal X-ray diffraction and UV-Vis-NIR spectroscopy. The Am(ODA)(C 2 O 4 )(H 2 O) 3 structure was similar to that established previously for Ln 3+ analogues, namely Ln(ODA)(C 2 O 4 )(H 2 O) x . These compounds were all isomorphous, had bridging C 2 O 4 2– and ODA 2– ligands, and crystallized as 2-dimensional extended solids. In addition, the Am 3 +–O bond distances could be predicted based on relative differences in Am 3+ and Ln 3+ 9-coordinate metal ionic radii. Overall, isolation of Am(ODA)(C 2 O 4 )(H 2 O) 3 showcased similarities in complexation and crystallization chemistry for Am 3+ and Ln 3+ .

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

Elucidating the Chemical Pathways Responsible for the Sooting Tendency of 1 and 2-phenylethanol

Yield Sooting Index (YSI) measurements have shown that oxygenated aromatic compounds (OACs) tend to have lower YSI than aromatic hydrocarbon (AHC) compounds. For example, typical AHCs such as toluene and ethyl benzene have a YSI of 170 and 216, respectively, in contrast, OACs such as phenol and anisole have a YSI of 81 and 111, respectively. However, this trend is not always true as was observed for the structural isomers 1-phenylethanol (1PE, YSI=142) and 2-phenylethanol (2PE, YSI=207), where 2PE contains a YSI more representative of AHCs than OACs. We applied flow reactor experiments and density functional theory (DFT) calculations to examine how oxygen functionality present in 1PE and 2PE alters the reaction pathways leading to the observed difference in soot formation. It was determined that the proximity of the oxygen functional group to the aromatic ring determines whether the oxygen remains attached to the primary reacting species (for 1PE) or is eliminated early in the combustion sequence (for 2PE). For these alcohols, preservation of the oxygen in the molecule leads to further OACs, while loss of the oxygen leads to AHCs and benzyl radical. The direct pathways to AHCs and benzyl radical result in the higher YSI observed for 2PE.

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

Mixing and detonation structure in a rotating detonation engine with an axial air inlet

High-fidelity simulations of an experimental rotating detonation engine with an axial air inlet were conducted. The system operated with hydrogen as fuel at globally stoichiometric conditions. Instantaneous data showed that the detonation front is highly corrugated, and is considerably weaker than an ideal Chapman–Jouguet wave. Regions of deflagration are present ahead of the wave, caused by mixing with product gases from the previous cycle, as well as the injector recovery process. It is found that as the post-detonation high pressure flow expands, the injectors recover unsteadily, leading to a transient mixing process ahead of the next cycle. The resulting flow structure not only promotes mixing between product and reactant gases, but also increases likelihood of autoignition. These results show that the detonation process is very sensitive to injector design and the transient behavior during the detonation cycle. Phase-averaged statistics and conditionally averaged data are used to understand the overall reaction structure. As a result, comparisons with available experimental data on this configuration show remarkable good agreement of the predicted reacting flow structure.

42 ENGINEERING↗
DOE OSTI2020

Identification of combustion mode under MILD conditions using Chemical Explosive Mode Analysis

Direct Numerical Simulations (DNS) data of Moderate or Intense Low-oxygen Dilution (MILD) combustion are analysed in this paper to identify the contributions of the autoignition and flame modes. This is performed using an extended Chemical Explosive Mode Analysis (CEMA) which accounts for diffusion effects allowing it to discriminate between deflagration and autoignition. This analysis indicates that in premixed MILD combustion conditions, the main combustion mode is ignition for all dilution and turbulence levels and for the two reactant temperature conditions considered. In non-premixed conditions, the preponderance of the ignition mode was observed to depend on the axial location and mixture fraction stratification. With a large mixture fraction lengthscale, ignition is more preponderant in the early part of the domain while the deflagrative mode increases further downstream. On the other hand, when the mixture fraction lengthscale is small, sequential autoignition is observed. Finally, the various combustion modes are observed to correlate strongly with mixture fraction where lean mixtures are more likely to autoignite while stoichiometric and rich mixtures are more likely to react as deflagrative structures.

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

Quantifying the effect of CO 2 gasification on pulverized coal char oxy-fuel combustion

Previous research has provided strong evidence that CO 2 and H 2 O gasification reactions can provide non-negligible contributions to the consumption rates of pulverized coal (pc) char during combustion, particularly in oxy-fuel environments. Fully quantifying the contribution of these gasification reactions has proven to be difficult, due to the dearth of knowledge of gasification rates at the elevated particle temperatures associated with typical pc char combustion processes, as well as the complex interaction of oxidation and gasification reactions. Gasification reactions tend to become more important at higher char particle temperatures (because of their high activation energy) and they tend to reduce pc oxidation due to their endothermicity (i.e. cooling effect). The work reported here attempts to quantify the influence of the gasification reaction of CO 2 in a rigorous manner by combining experimental measurements of the particle temperatures and consumption rates of size-classified pc char particles in tailored oxy-fuel environments with simulations from a detailed reacting porous particle model. The results demonstrate that a specific gasification reaction rate relative to the oxidation rate (within an accuracy of approximately +/- 20% of the pre-exponential value), is consistent with the experimentally measured char particle temperatures and burnout rates in oxy-fuel combustion environments. Conversely, the results also show, in agreement with past calculations, that it is extremely difficult to construct a set of kinetics that does not substantially overpredict particle temperature increase in strongly oxygen-enriched N2 environments. This latter result is believed to result from deficiencies in standard oxidation mechanisms that fail to account for falloff in char oxidation rates at high temperatures.

42 ENGINEERING↗
DOE OSTI2022

Experimental and kinetic modeling study of the low- temperature and high-pressure combustion chemistry of straight chain pentanol isomers: 1-, 2- and 3-Pentanol

Pentanols have received significant attention as a potential alternative fuel or fuel additive owing to their high energy densities and low vapor pressure. The development of robust chemical kinetic models for alternative fuels which can provide accurate and efficient predictions of combustion performance across a wide range of engine relevant conditions is important in developing cleaner, more efficient combustors. Although the high temperature oxidation kinetics of pentanol isomers has been researched considerably, their low temperature combustion chemistry needs further investigation. While previously proposed low temperature mechanisms for 1-pentanol based on analogy and rate rules need further refinement, the low temperature oxidation kinetics of 2-pentanol and 3-pentanol has not been studied previously by any means, experimentally or theoretically. A newly developed kinetic mechanism is presented in this work for the three straight chain pentanol isomers: 1-, 2- and 3-pentanol. Low temperature kinetics is based on a recent study by Lockwood et al., 2022 [20] involving theoretical calculations at the CCSD(T)/cc-pV∞Z level of theory for the oxidation pathways involving alcohol peroxy radicals. Rate of production analyses performed in this study highlight the importance of the newly added pressure-dependent reactions of the α-alcohol peroxy radical forming an RO 2 adduct. While the α-alcohol fuel radical reacts with O 2 to directly decompose via a chemically activated pathway at low pressures, the formation of the RO 2 adduct is favored at high pressures. Furthermore, the detailed model is comprehensively validated against new ignition experiments at low temperature and high pressure, together with the wide range of data available in the literature. Both qualitative and quantitative predictions of the experimental data using the proposed kinetic model are satisfactory for all three pentanol isomers studied here.

1-pentanol↗
DOE OSTI2024

An improved semi-global intrinsic kinetics model for high temperature carbon oxidation

Measurements of the oxidation rates of various forms of carbon (soot, graphite, coal char) have often shown an unexplained attenuation with increasing temperatures in the vicinity of 2000 K, even when accounting for diffusional transport limitations and gas-phase chemical effects (e.g. CO 2 dissociation). With the development of oxy-fuel combustion approaches for pulverized coal utilization with carbon capture, high particle temperatures are readily achieved in sufficiently oxygen-enriched environments. Here, in this work, a new semi-global intrinsic kinetics model for high temperature carbon oxidation is created by starting with a previously developed 5-step mechanism that was shown to reproduce all major known trends in carbon oxidation, except for its high temperature kinetic falloff, and incorporating a recently discovered surface oxide decomposition step. The predictions of this new model are benchmarked by deploying the kinetic model in a steady-state reacting particle code (SKIPPY) and comparing the simulated results against a carefully measured set of pulverized coal char combustion temperature measurements over a wide range of oxygen concentrations in N 2 and CO 2 environments. The results show that the inclusion of the spontaneous surface oxide decomposition reaction step significantly improves predictions at high particle temperatures. Furthermore, the simulations reveal that O atoms released from the oxide decomposition step enhance the radical pool in the near-surface region and within the particle interior itself. Incorporation of literature rates for O and OH reactions with the carbon surface results in a reduction in the predicted radical pool concentrations and a very minor enhancement of the overall carbon oxidation rate.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2024

Styrene Thermal Decomposition and Its Reaction with Acetylene under Shock Tube Pyrolysis Conditions: an Experimental and Kinetic Modeling Study

Styrene is an important compound for polymer production and a key intermediate in gas-phase kinetics of polycyclic aromatic hydrocarbons (PAHs). For the first time, the pyrolysis of styrene with and without the presence of acetylene is investigated in a single-pulse shock tube coupled to gas chromatography and mass spectrometry. For each reaction system, quantitative speciation profiles are probed within the temperature range of 1100-1730 K, nominal pressure of 20 bar, and reaction duration of similar to 4 ms. A kinetic model is built to simulate the results. The model explains how styrene is consumed under high-pressure pyrolytic conditions, how the secondary chemistry of intermediate products affect subsequent PAH formation, and how acetylene addition alters the reaction pathways. Throughout the temperature range, styrene breakdown is dominated by the bimolecular interaction between styrene and hydrogen atom, which produces benzene+vinyl or phenyl and ethylene through the stabilization of 2-phenylethyl and its subsequent dissociation. As a result, large amounts of phenyl accumulate, which react with styrene to form C14H12 species while simultaneously releasing H atoms through addition/elimination reactions. The reactivity of fuel consumption is preserved by the regeneration of H atoms as chain carriers. Several C14H10 compounds are formed as a result of the following breakdown of the C14H12 isomers, particularly stilbene, 1,1-diphenyl ethylene, and 9-methyl-9H-fluorene. The presence of acetylene as a co-reactant with styrene allows the Hydrogen-Abstraction-Acetylene-Addition (HACA) pathway to proceed from phenyl radical to enhance the production of phenylacetylene at very low temperatures and acenaphthylene. This hinders the formation of C14H12 isomers, exclusive products from pure styrene dissociation by competing with the styrene+phenyl routes.

Kinetic Modeling↗
DOE OSTI2024

High resolution numerical simulations of methane pool fires using adaptive mesh refinement

The ability to accurately predict the structure and dynamics of pool fires using computational simulations is of great interest in a wide variety of applications, including accidental and wildland fires. However, the presence of physical processes spanning a broad range of spatial and temporal scales poses a significant challenge for simulations of such fires, particularly at conditions near the transition between laminar and turbulent flow. Here, in this study, we examine the transition to turbulence in methane pool fires using high-resolution simulations with multi-step finite rate chemistry, where adaptive mesh refinement (AMR) is used to directly resolve small-scale flow phenomena. We perform three simulations of methane pool fires, each with increasing diameter, corresponding to increasing inlet Reynolds and Richardson numbers. As the diameter increases, the flow transitions from organized vortex roll-up via the puffing instability to much more chaotic mixing associated with finger formation along the shear layer and core collapse near the inlet. These effects combine to create additional mixing close to the inlet, thereby enhancing fuel consumption and causing more rapid acceleration of the fluid above the pool. We also make comparisons between the transition to turbulence and core collapse in the present pool fires and in inert helium plumes, which are often used as surrogates for the study of buoyant reacting flows.

42 ENGINEERING↗
DOE OSTI2026

From PAH to fullerenes: Closing a nano bowl with a nano lid

Quantum chemical DLPNO-CCSD(T)/cc-pVDZ//B3LYP/6–31G(d) calculations have been performed to unravel the formation mechanism of buckminsterfullerene (C 60 ) via the reaction of the C 40 nano bowl (C 40 H 10 ) and corannulene (C 20 H 10 ). The generated potential energy surfaces and molecular properties were further utilized to evaluate equilibrium constants and rate constants of elementary chemical reactions involved in the C 60 synthesis. The overall C 40 H 10 + C 20 H 10 → C 60 + 10H 2 reaction is shown to be highly exoergic and hence thermodynamically favorable at temperatures above 700 K and a kinetically feasible pathway under high-temperature conditions was revealed. This route involves hydrogen atom abstraction steps to activate closed-shell reactants/intermediates alternating with cyclodehydrogenation reactions eventually zipping the edges between the reacting C 40 and C 20 units by consecutive closures of six- and five-membered rings between them. The reaction is driven/catalyzed by hydrogen atoms which carry out the hydrogen abstractions from C 60 H x and are later recovered on the cyclodehydrogenation stages. The initial association reaction, C 40 H 9 + C 20 H 10 → C 60 H 18 + H, linking the two units by a covalent C-C bond appears to represent the kinetic bottleneck of the whole multistep process. This reaction is fast at low temperatures but slows down and has its equilibrium shifted toward the reactants at high temperatures. Here, the feasibility of the proposed mechanism corroborates the hypothesis that C 60 can be produced through a series of elementary reactions typical for the PAH growth.

Equilibrium constant↗
DOE OSTI2024

Comparison of volatiles evolving from selected highland and mare lunar regolith simulants during vacuum sintering

Volatiles evolving from JSC-1A, NU-LHT-4M and CSM-LHT-1G lunar regolith simulants during in vacuo thermal processing were analyzed using mass spectrometry as a function of temperature. Two high-fidelity simulants, JSC-1A (mare) and NU-LHT-4M (highland), were compared to a newly developed CSM-LHT-1G highland simulant, modified to closely match lunar geochemistry. Large autogenous gas loads were observed for all investigated materials. Mineralogical knowledge was used to identify and attribute individual volatile species to reacting, transforming, or decomposing constituents (hydrates, carbonates, sulfates, sulfides, clays, etc.) of the respective regolith simulant in the self-generated gas environment. Cumulative mass losses for individual simulant components as a function of temperature were quantified using mass spectrometry in conjunction with thermogravimetric analysis. Investigation of the four components of CSM-LHT-1G – anorthosite, basalt, augite, and glass – aided the attribution of volatile species to specific compounds and their respective sources. The results showed significant decomposition of non-lunar phases present in the man-made regolith simulants below the typical glass crystallization temperatures, which paves the way to devising methods for enhancing the fidelity of the simulants. Finally, high gas loads and corrosive gases (HF and HCl) were recognized as potential hazards, pertaining to the development of large testbed facilities.

42 ENGINEERING↗
DOE OSTI2023

Persistent radicals in irradiated imidazolium ionic liquids probed by EPR spectroscopy

Long-lived radicals were observed in irradiated room temperature ionic liquids (RTILs) composed of the bis(trifluoromethylsulfonyl)imide anion (Tf 2 N - ) with 1-hexyl-3-methylimidazolium (hmim + ) and1-butyl-3-methylimidazolium (bmim+) cations. The EPR signal intensity increases within hours and the spectral pattern changes during the time after irradiation. The kinetics data obtained indicate the existence of at least two distinct radical cations that have different formation and decay rates. We demonstrate that oxygen does not react rapidly with the radical species formed. The bmim + Tf 2 N - was selectively deuterated at various positions which allowed us to suggest possible structures of the stable radicals formed. The first structure is a radical cation containing 2 nitrogens and 6 protons all with ca. 8.2 Gauss hyperfine splittings, and 2 protons with 2.8 Gauss splitting. The structure of the second radical cation is similar, but characterized by an odd number of hydrogens with ca. 8.2 Gauss splitting. Extensive quantum chemistry calculations were performed to attempt to identify the structure of these persistent radicals. The most likely candidates are imidazole radical cations having methyl groups at the nitrogen atoms and substituents in the second position of the imidazole ring.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

Pulse radiolysis and transient absorption spectra of aqueous solutions of sodium sulfamate

Chemical kinetics for the reactions of sulfamate ions (NH 2 SO 3 − ) with the primary products of water and nitric acid radiolysis were measured in aqueous solutions at ambient temperature. Using time-resolved electron pulse radiolysis techniques with a custom multichannel detection system, we examined the reactivity of NH 2 SO 3 − with the hydroxyl radical ( • OH), hydrogen atom (H • ), and nitrate radical (NO 3 • ). The sulfamate ion was found to react with • OH and H • with second-order rate coefficients of k • OH = (5.60 ± 0.04) × 10 6 M −1 s −1 and k H • = (7.96 ± 0.10) × 10 6 M −1 s −1 , respectively, and with NO 3 • with a rate coefficient of k NO 3 • = (1.67 ± 0.06) × 10 7 M −1 s −1 . The reactions of NH 2 SO 3 − with • OH and H • resulted in the formation of two transient radical species, one with maximum absorbance at 300 nm and a second with maxima at both 300 nm and 600 nm. These spectra are tentatively assigned to • NH 2 SO 3 and • NHSO 3 − , respectively. By measuring the absorbance of these radicals as a function of pH, the radical pK a was determined to be 9.5 ± 0.1. Overall, this work has implications for the longevity and performance of ferrous sulfamate, Fe(NH 2 SO 3 ) 2 , as a plutonium reductant in the reprocessing of used nuclear fuel.

Conrad, Jacy K. [Idaho National Laboratory (INL), ↗
DOE OSTI2020

Characterization and verification of a two-body wave energy converter with a novel power take-off

The lack of high efficient, predictable and reliable power take-off (PTO) systems limits developments of ocean wave energy technology. In this paper, a two-body self-reacting wave energy converter (WEC) with a novel PTO is designed, modelled and implemented for efficiency enhancement. A novel mechanical motion rectifier (MMR) using a ball screw mechanism and an enclosed gear set is integrated to improve the energy harvesting efficiency and reliability by rectifying the oscillatory wave motion into unidirectional rotation of the generator. Detailed design and dynamic modelling for the proposed WEC are presented. A prototype of the PTO is tested in a dry lab to characterize and refine the dynamic modelling. The characterized PTO model is combined with the WEC model to create an overall system model. A water tank test is conducted to verify the overall system dynamics, which proves the accuracy of the model and shows the advantages of the proposed WEC on efficiency and predictability. Following the method of how the WEC system is characterized, performance prediction of the proposed WEC with MMR PTO can be achieved with high accuracy.

16 TIDAL AND WAVE POWER↗
DOE OSTI2025

Alloy selective optical sorting of mixed post-consumer aluminum scrap streams

Shredded post-consumer non-ferrous scrap stream, also known as Zorba, contains a mixture of cast and wrought aluminum pieces with very different compositions. Cast Al pieces, with their high Si, Cu and Fe content, are a major contaminant in wrought scrap fraction, which results in downcycling of the mixed cast + wrought scrap into non-structural cast Al alloys and parts. Here, in this paper, we introduce a chemical treatment method to color-code scrap aluminum pieces by alloy family and demonstrate low-cost optical sorting of cast from wrought pieces to upgrade the scrap stream. We utilized non-acidic chemical solutions that react with (i.e., etch) the scrap pieces to produce colors based on the Al alloy chemistry of a given piece. Cast pieces with high Si and Cu fractions turned black, whereas the much leaner wrought pieces remained unreacted. We showed > 95% sorting efficiency of mixed cast and wrought pieces using a repurposed low-cost optical sorter originally designed for food sorting. We also colored wrought Al pieces by alloy families, such as 5xxx and 6xxx, using a two-step chemical etching technique, which has the potential to create a circular supply chain in which wrought aluminum alloys are sorted from the mixed scrap stream and recycled back to high-value wrought products such as sheets, extrusions, and forgings with minimal contamination from cast scrap.

Aluminum↗
DOE OSTI2023

Utilizing metal cation reactions with carbonyl sulfide to remove isobaric interferences in tandem inductively coupled plasma mass spectrometry analyses

Carbonyl sulfide (OCS) was used as a reaction gas to investigate gas phase metal (M + ) ion-molecule reactions using the Agilent 8900 inductively coupled plasma tandem mass spectrometer (ICP-MS/MS) to yield insight on how this gas may be used to remove isobaric interferences in analytical measurements. The experimental work was paired with density functional theory (DFT) calculations of the reaction enthalpy to predict whether M + will react with OCS. A multi-element standard containing 46 elements ranging from 9 to 208 u was analyzed in the presence and absence of OCS. When a reaction was observed, the dominant product was the sulfide (MS + ). Oxide products were also observed for many M + but formation was less efficient with OCS than previously observed with other reaction gases. This is likely due to the weaker OC-S bond that makes MS + formation more favorable. Increasing the flow rate from 0.1 to 0.2 mL/min (corresponding to a change in reaction gas pressure from 0.35 to 0.53 Pa (2.6 to 4.0 mTorr)) generally resulted in greater MS + production, including the secondary product MS 2 + for a few cations. The early lanthanide series ions (La + , Ce + , Pr + and Nd + ) produced greater quantities of MO + at the higher pressure, although MS + products were still the dominant product. The DFT-predicted reaction enthalpies were consistent with the observed sulfide formation, with an accuracy >90%; however, model predictions were less accurate for the minor and higher order products (< 77% for MO + ). Finally, the work presented here continues a systematic study of ion-molecule reactions in ICP-MS/MS to understand and develop new and novel ways to analyze complex mixtures with minimal pre-analysis treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗