Hydrogen Abstraction Reactions Research Articles

Systematic study on the hydrogen abstraction reactions from oxygenated compounds by H and HO2

AbstractTo extend the rule‐based approach for hydrogen abstraction reactions from oxygenated compounds, a systematic investigation was performed to examine the reactivity of gas‐phase hydrogen abstraction reactions from alkyl groups (methyl and ethyl groups) bound to oxygen atoms in five types of oxygenated compounds (alcohols, ethers, formate esters, acetate esters, and carbonate esters) by H atoms and HO2 radicals comprehensively considering rotational conformers. Quantum chemical calculations were conducted at the CBS‐QB3 level for stationary points. Rate constants were determined employing conventional transition state theory (TST). For hydrogen abstraction reactions by H, the rotational conformer distribution partition function was employed to approximate partition functions, owing to the similarity in vibrational energy‐level structures among conformers. In hydrogen abstraction reactions by HO2, the vibrational structures of transition‐state (TS) conformers varied significantly due to the hydrogen bonding, leading to an inappropriate evaluation of rate constants when using the lowest‐energy conformer as a representative. Therefore, the rate constants were calculated by the multi‐structural TST. It was revealed that the differences in functional groups containing O atoms mainly affect the bond dissociation energies of the C–H bonds and the activation energies of hydrogen abstraction reactions only when the C atoms are adjacent to the O atoms. Additionally, it was found that hydrogen bonds formed in the TSs show minor effect on rate parameters for the overall rate constants, apart from the reduction of the pre‐exponential factors for the H‐abstraction reactions from the methylene position of ethyl groups. The comparison with the rate constants from previous studies showed reasonable results, indicating that the rate constants in this study, which thoroughly consider rotational conformers, can be the current best estimates.

Relative Humidity and Altitude Effects on the Water-Mediated Hydrogen Abstraction Reaction of Furan by the Hydroxyl Radical

Relative Humidity and Altitude Effects on the Water-Mediated Hydrogen Abstraction Reaction of Furan by the Hydroxyl Radical

Hydrogen abstraction reactions by NH2 radicals from C3-C6 Cycloalkanes: A theoretical study

Amino (NH2) radicals are crucial in ammonia pyrolysis and oxidation, and their reactions in NH3-dual-fuel combustion are well-recognized. We theoretically investigated the reactions of NH2 radicals with C3-C6 cycloalkanes – a component type of gasoline, using the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ level of theory. Canonical transition state theory with corrections for hindered internal rotation and Eckart tunneling effects was employed to gain high-pressure limiting rate constants over 500 – 2000 K. Our calculated rate constant for NH2 with cyclohexane matches the experimental measurement, though experimental data for other reactions are limited. The Arrhenius parameters for the studied reactions are also provided.

Comprehensive Multipath Variational Kinetics Study on Hydrogen Abstraction Reactions from Three Typical Dimethylcyclohexane Isomers by Hydroxyl Radicals: from the Electronic Structure to Model Applications.

Cycloalkanes serve as an important class of chemical components in both fossil and alternative transportation fuels and have attracted considerable attention from the combustion community. Hydrogen abstractions from cycloalkanes by hydroxyl radicals initiate the fuel decomposition process and trigger off the subsequent chain reactions and thus play an important role in both combustion and atmospheric chemistry. The target of this study is to fill the vacancy in kinetics data toward the H-abstraction reactions by hydroxyl radical from three typical dimethylcyclohexane isomers through first-principles and direct dynamics. The rate constants involving 18 elementary reactions in total were accurately determined by the multipath canonical variational transition state theory with the multidimensional small-curvature correction for tunneling (MP-CVT/SCT), over a broad temperature range of 200-2000 K. The significant roles of multistructural torsional anharmonicity and recrossing effects were stressed per abstraction site, while the quantum tunneling effect was found to be slight at temperatures of interest in combustion. The discrepancies observed among different reaction systems at a similar abstraction site highlight the fuel molecular effects on site-specific rate constants. The comparison results of total rate constants given by different dynamics approaches prove the importance of considering the torsional anharmonicity, recrossing, and tunneling effects, and the robust feature of the simplified MS-CVT/SCT. The calculated total constants for dimethylcyclohexane isomers by OH are consistent with those measured for methylcyclohexane and 1,4-dimethylcyclohexane at low temperatures. The branching ratio analysis confirms the predominant role of the tertiary abstraction at low-to-intermediate temperatures and its growing competition with distinct secondary abstractions as temperature increases. The calculated rate constants were eventually fitted into the analytical expressions and incorporated into the kinetic models to learn about the influences on modeling performance.

With a little help from our (AI) friend: A general transition state sampling method for tropospheric hydrogen abstraction reactions

Due to their pivotal role in atmospheric processes, hydrogen abstraction reactions are vital in the study of tropospheric chemistry. In this work, we present an algorithm that generates a large number of chemically sound geometries for the optimization of transition states (TSs) of tropospheric bimolecular H abstraction reactions. The code, which was developed in the early stages with the help of artificial intelligence (AI), automatically detects the active H atoms of the molecule and can be used with the OH, Cl, and NO3 oxidants. Given the ubiquity of H transfer reactions in various fields, the algorithm was designed in general terms to facilitate easy adaptation to other oxidants, thus allowing for a broader range of applications. As a result of its use, a much greater number of TSs is predicted when compared with previous theoretical studies of six oxidation reactions. In addition to improving our understanding of the H-abstraction process, obtaining an increased number of TSs is also fundamentally important in calculating more accurate rate constants and atmospheric lifetimes for volatile organic compounds. The simplicity and significance of such a tool in the context of environmental chemistry should make it appealing to researchers of all backgrounds.

Hydrogen abstraction reaction mechanism of oil-rich coal spontaneous combustion

Oil-rich coal is a type of coal with a hydrogen-rich structure, making it susceptible to spontaneous combustion at low temperatures. To investigate the process of hydrogen production through the low-temperature oxidation of oil-rich coal, nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR) experiments were conducted, along with quantum chemical simulations, to identify the dynamic changes in functional groups during low-temperature oxidation. The experimental results indicate that oil-rich coal primarily comprises hydrogen-containing structures, such as aromatic hydrocarbons and aldehyde groups. Based on the observed patterns of the functional group changes, three stages of hydrogen generation during the low-temperature oxidation of oil-rich coal were deduced. Furthermore, quantum chemical simulations were employed to model the target functional groups' structural changes during oil-rich coal's low-temperature oxidation. Combining the results of the experiments and simulations revealed the primary mechanism behind the low-temperature oxidation of oil-rich coal, leading to hydrogen production. This study identified the reaction of methylmethylene side chains forming aldehyde groups as a precursor to hydrogen. The simultaneous oxidation and structural interactions eventually result in the formation of hydrogen. These findings provide a more profound insight into the mechanism behind the spontaneous combustion of coal oxidation and provide a theoretical foundation for developing effective prevention and management technologies for the spontaneous combustion of oil-rich coal.

Theoretical and kinetic study of the hydrogen abstraction reactions of ethyl propionate

Ethyl propionate shows great promise as a biodiesel molecule model. However, the current oxidation kinetic model falls short in accurately predicting its combustion behavior. Therefore, this study employed ab initio quantum chemistry methods to analyze the hydrogen abstraction reactions of ethyl propionate with various reactive radicals, including OH, O, H, CH3, C2H3, C2H5, HO2, CH3O and CH3O2, which play a critical role in refining the oxidation kinetics. Theoretical calculations were conducted to determine the rate constants and branching ratios for these reactions at temperatures ranging from 500 K to 2500 K using transition state theory, quasi-rigid rotor harmonic oscillator model, and tunneling correction. After updating the kinetics of hydrogen abstraction reactions in the oxidation mechanism proposed by Metcalfe et al., the modified model was validated by comparing the simulated mole fraction evolutions of ethyl propionate and major products in a jet-stirred reactor, ignition delay in a closed homogeneous batch reactor, and laminar flame speed with experimental data. The findings indicate that the modified model reliably reproduces the experimental data and significantly improves the prediction accuracy for low-temperature combustion of ethyl propionate when compared to the original model.

An ONIOM-Based High-Level Thermochemistry Study on Hydrogen Abstraction Reactions of Large Straight-Chain Alkanes by Hydrogen, Hydroxyl, and Hydroperoxyl Radicals

Accurate thermochemical data are of great importance in developing quantitatively predictive reaction mechanisms for transportation fuels, such as diesel and jet fuels, which are primarily composed of large hydrocarbon molecules, especially large straight-chain alkanes containing more than 10 carbon atoms. This paper presents an ONIOM[QCISD(T)/CBS:DFT]-based theoretical thermochemistry study on the hydrogen abstraction reactions of straight-chain alkanes, n-CnH2n+2, (n = 1–16) by hydrogen (H), hydroxyl (OH), and hydroperoxyl (HO2) radicals. These reactions, with n ≥ 10, pose significant computational challenges for prevalent high-level ab initio methods. However, they are effectively addressed using the ONIOM-based method. One notable aspect of this study is the consideration of the high symmetry of straight-chain alkanes. This symmetry allows us to study half of the reactions, employing a generalized approach. Therefore, a total of 216 reactions are systematically studied for the three reaction systems. Our results align very well with those from the widely accepted high-level QCISD(T)/CBS method, with discrepancies between the two generally less than 0.10 kcal/mol. Furthermore, we compared large straight-chain alkanes (n-C16H34 and n-C18H38) with large methyl ester molecules (C15H31COOCH3 and C17H33COOCH3) to elucidate the impact of functional groups (ester group and C=C double bond) on the reactivity of the long-chain structure. These findings underscore the accuracy and efficiency of the ONIOM-based method in computational thermochemistry, particularly for large straight-chain hydrocarbons in transportation fuels.

Modeling the kinetics of hydrogen abstraction reactions in nitrogen-containing compounds via group additivity.

New group additivity values are presented to enable the modeling of a broad range of intermolecular hydrogen abstraction reactions involving nitrogen-containing compounds. From a dataset of 316 reaction rate coefficients calculated at the CBS-QB3 level of theory in the high-pressure limit, 76 group additivity values and 14 resonance corrections have been estimated. The influence of substituents on both the attacked hydrogen and attacking radical, being a carbon or nitrogen atom, has been investigated systematically. The new group additivity models can be applied to approximate the Arrhenius parameters of hydrogen abstraction reactions of nitrogen-containing compounds by hydrogen atoms, carbon-centered and nitrogen-centered radicals in the 300-1800 K temperature range. Complementary to the group additivity model, correlations for the tunneling coefficients, which depend on both the temperature and the activation energy of the reaction in the exothermic direction, have been generated. The good performance of the new group additivity schemes has been demonstrated using a test set of reactions. At 1000 K, the rate coefficients for all test set reactions are approximated on average within a factor of 1.45, 1.47 and 1.34, for the hydrogen abstractions with a reactive center of the type H-H-N, N-H-N and C-H-N respectively.

Kinetic study of the CN + C2H6 hydrogen abstraction reaction based on an analytical potential energy surface.

The temperature dependence of the thermal rate constants and kinetic isotope effects (KIE) of the CN + C2H6 gas-phase hydrogen abstraction reaction was theoretically determined within the 25-1000 K temperature range, i.e., from very low- to high-temperature regimes. Based on a recently developed full-dimensional analytical potential energy surface fitted to highly accurate explicitly correlated ab initio calculations, three different kinetic theories were used: canonical variational transition state theory (CVT), quasiclassical trajectory theory (QCT), and ring polymer molecular dynamics (RPMD) method for the computation of rate constants. We found that the thermal rate constants obtained with the three theories show a V-shaped temperature dependence, with a pronounced minimum near 200 K, qualitatively reproducing the experimental measurements. Among the three methods used in this work, the QCT and RPMD methods have the best agreement with the experiment at low and high temperatures, respectively, while the CVT model shows the largest discrepancies. The significant increase in the rate constant at very low temperatures in this very exothermic and practically barrierless reaction could be attributed to the large value of the impact parameter, possibly ruling out the role of the tunneling effect and the intermediate complexes in the entrance channel. The theoretical H/D KIE depicted a "normal" behaviour, i.e., values greater than unity, emulating the experimental measurements and improving previous theoretical results. Finally, the discrepancies between theory and experiments were analysed as a function of several factors, such as limitations of the kinetics theories and the potential energy surface, as well as the uncertainties in the experimental measurements.

Theoretical Kinetic Study on Hydrogen Abstraction Reactions from n-Pentane by NO2.

The interaction of fuel with NOx chemistry is important for the construction of the reaction mechanism and engine application. In this work, the reaction pathways of nC5H12 + NO2 were studied by high-level electronic structure calculations (DLPNO-CCSD(T)-F12/cc-pVTZ-F12//B2PLYPD3/cc-pVTZ). The rate constants were calculated by using the multistructural canonical transition-state theory with the Eckart tunneling method (TST/MS-T/ET). The studied condition is in a wide temperature range of 298-2400 K. The influence of MS-T anharmonicity and tunneling effect will be clarified for these site-specific H-abstraction pathways. The result reflects the large deviation introduced by the treatment of MS-T anharmonicity, especially at a high temperature. For the same type of reactions, the rate constants of H-abstraction both occurring at the secondary carbon are not almost identical. The branching ratios show that abstraction from the secondary site forming cis-HONO (R2c) contributes 36-78% to nC5H12 consumption in the temperature range of 298-2400 K. The current results show that the multistructural torsional anharmonicity has a crucial influence on the accurate estimation of branching ratios.

DFT studies of solvent effect in hydrogen abstraction reactions from different allyl-type monomers with benzoyl radical

Inert allyl-type monomers have been widely documented due to reduce degradation chain transfer. Recently, we and others discovered that the [3 + 2] cyclization reaction process by a photo-driven radical reaction, which can accelerate the polymerization. It was discovered that allyl ether monomers had much higher reactivity than other allyl monomers in the suspension photopolymerization initiated by Type I photoinitiator. Since the hydrogen abstraction reaction (HAR) is the initial step of cyclization, and in order to clarify the influence of solvents effect, three allyl-type monomers were employed, containing “O”, “N” and “S” atom as hydrogen donors. The benzoyl radical obtained from cleavage of photoinitiator was chosen as hydrogen acceptors. We explored the hydrogen abstraction reaction in different solvents (methanol, water and DMSO) by quantum chemistry for geometry and energy. An investigation was undertaken regarding the structural orbital by electrostatic potential (ESP) and topological analysis (ELF and LOL). The findings were also combined with the distortion model and transition state theory. We obtained the molecular interactions used independent gradient method in the Hirshfeld molecular density partition (IGMH). The Eckart’s correction allowed to examine the driving factors of the hydrogen abstraction reaction tunnels and these reactions constant rates are determined in the range of 500–2500 K depending on the modified Arrhenius form in different solvents effect. Our results can provide an answer for the different reactivities.

Theoretical study on hydrogen abstraction reactions from pentane isomers by NO2

The rate constants for the H-abstraction reactions of C5H12 + NO2 are calculated by high-accuracy electronic structure calculations and transition state theory (TST). The investigation includes three pentane isomers, neopentane, n-pentane, and iso-pentane, each of which leads to the formation of three different HONO isomers, namely cis-HONO, trans-HONO, and HNO2. The lowest energy conformers of all relevant species are determined through geometry optimization, frequency analysis, and one-dimensional hindered rotor scanning at the M06-2X/6-311++G(d,p) level of theory, and are further re-optimized using the B2PLYP-D3/cc-pVTZ method. The single point energies of all the reactants, products, and transition states are obtained at the DLPNO-CCSD(T)/CBS level of theory. Traditional transition state theory was employed to derive the rate constants, which were then fitted to obtain the kinetic parameters in the Arrhenius expression. Simulation results show improved performance in ignition delay times and oxidation species prediction, when the calculated reaction rate constants are implemented in the literature n-pentane kinetic models. The results offer enhanced comprehension of the chemistry of C5H12 + NO2, and will aid in the understanding of the mutual reactions of large hydrocarbon fuels and NOx.

Kinetic study of hydrogen abstraction reactions from n-propyl/n-butylcyclohexane by hydrogen atom

Hydrogen abstraction reactions of alkylated cycloalkane by radicals play a fundamental role in combustion and atmospheric chemistry. In this work, we select two representative molecules in alkylated cycloalkane fuels, n-propylcyclohexane (nPCH) and n-butylcyclohexane (nBCH), to investigate the kinetics of their hydrogen abstraction reactions with hydrogen atom. The rate constants over a broad temperature range of 298–2000 K were calculated by using canonical transition state theory coupled with the multistructural torsional anharmonicity effect (TST/MS-T). We stress the particular importance of considering the MS-T anharmonicity for the investigated species involved in the H-abstraction pathways. Due to the approximate cancelation of the anharmonicity factor between the transition-state species and the reactant, the anharmonicity factors for reactions are spread over a narrower range of 0.7–3.3. The anharmonicity will slightly accelerate the H-abstraction for the nBCH system over the whole temperature range. The current results show that the multistructural torsional anharmonicity will influence the accurate estimation of competing relationships. We found that the total H-abstraction rate constants of the nBCH system by the TST/MS-T method are larger by factors of 1.2–1.3 than those for the nPCH system. The present data show that nPCH + H channels are less important by factors of 1.41–5.48 than currently estimated by the commonly used nPCH pyrolysis model. The H-abstraction ratios from the cyclic ring and side chain groups reveal that the rate rule for secondary carbon in chain alkanes does not represent the reactivity of all cycloalkanes well, e.g. the ratio between the cyclic ring and side chain group is high up to 2.8.

Machine learning rate constants of hydrogen abstraction reactions between ester and H atom

The rate constants of hydrogen abstraction reactions of alkyl ester by H atom are crucial for optimizing combustion reaction network and improving combustion efficiency of biodiesel. Due to the lack of experimental and theoretical rate coefficients data for some reactions - such as hydrogen abstraction of large biodiesel molecules by free radicals - machine learning provides a viable alternative to predict rate constants. In this study, three different machine learning (ML) methods - feedforward neural network (FNN), extreme gradient boosting (XGB) and XGB-FNN hybrid model - were used to predict rate constants of the reactions between alkyl ester and H atom. The rate constants of 41 reactions between H + CnH2n+1COOCmH2m+1 (n = 0–5, m = 1, 2) were calculated by the Master Equation System Solver (MESS) program over a temperature range of 300–2000 K for model training. The results showed that the XGB-FNN model with 8 descriptors has better overall performance than the other two ML methods. The average deviation of XGB-FNN model on the test set is 33.56% by performing leave one out (LOO) cross validations. The rate constants of the H + methyl decanoate (MD) reactions over a temperature range of 300∼2000 K were predicted by the XGB-FNN model, which follow well the modified three-parameter Arrhenius equation and agree well with theoretical values, indicating that the hybrid XGB-FNN model is robust in predicting the rate constants of alkyl ester and H atom in the temperature range of combustion. The present ML method in this study is supposed to be able to provide accurate and affordable rate constants prediction of larger systems, the molecular sizes of which are comparable to those of the dominant components of real biodiesel. That is important for the development of biodiesel kinetic models.

Theoretical kinetics analysis of the OH + CH3OH hydrogen abstraction reaction using a full‐dimensional potential energy surface

AbstractBased on an analytical full‐dimensional potential energy surface (PES), named PES‐2022, fitted to high‐level ab initio calculations previously developed by our group and specifically developed to describe this polyatomic reactive process, an exhaustive kinetics analysis was performed in the temperature range 50–2000 K, that is, interstellar, atmospheric and combustion conditions. Using the competitive canonical unified theory with multidimensional tunneling corrections of small curvature, CCUS/SCT, and low‐ and high‐pressure limit (LPL and HPL) models, in this wide temperature range we found that the overall rate constants increase with temperature at T > 300 K and T < 200 K, showing a V‐shaped temperature dependence, reproducing the experimental evidence when the HPL model was used. The increase of the rate constant with temperature at low temperatures was due to the strong contribution of the tunneling factor. The title reaction evolves by two paths, H2O + CH2OH (R1) and H2O + CH3O (R2), and the branching ratio analysis showed that the R2 path was dominant at T < 200 K while the R1 path dominated at T > 300 K, with a turnover temperature of ∼260 K, in agreement with previous theoretical estimations. Three kinetics isotope effects (KIEs), 13CH3OH, CH318OH, and CD3OH, were theoretically studied, reproducing the experimental evidence. The kinetics analysis in the present paper together with the dynamics study previously reported showed the capacity of the PES‐2022 to understand this important chemical process.

A Theoretical Study of Hydrogen Abstraction Reactions in Guanosine and Uridine.

All practically possible hydrogen abstraction reactions for guanosine and uridine have been investigated through quantum chemical calculations of energy barriers and rate constants. This was done at the level of density functional theory (DFT) with the ωB97X-D functional and the 6-311++G(2df,2pd) Pople basis set. Transition state theory with the Eckart tunneling correction was used to calculate the rate constants. The results show that the reaction involving the hydrogen labelled C4' in the ribofuranose part has the largest rate constant for guanosine with the value 5.097×1010 L mol-1s-1 and the largest for uridine with the value 1.62×1010 L mol-1s-1. Based on the results for these two nucleosides, there is a noticeable similarity between the rate constants in the ribofuranose part of the molecule, even though they are bound to two entirely different nucleobases.

Hydrogen-Donor-Controlled Polybrominated Dibenzofuran (PBDF) Formation from Polybrominated Diphenyl Ether (PBDE) Photolysis in Solutions: Competition Mechanisms of Radical-Based Cyclization and Hydrogen Abstraction Reactions.

Polybrominated dibenzofurans (PBDFs) are characteristic dioxin-like products of polybrominated diphenyl ether (PBDE) photolysis. In this study, competition mechanisms of radical-based cyclization and hydrogen abstraction reactions are proposed in PBDF formation. Commonly, the ortho C-Br bond dissociation during photolysis generates aryl radicals, which undergo intramolecular cyclization to form PBDFs or hydrogen abstraction with hydrogen donors (such as organic solvents and water) to form lower brominated PBDEs. By using 2,4,4'-tribromodiphenyl ether (BDE-28) as the model reactant, the experimental PBDF formation ratios in various solutions are explained quantitatively by the calculated rate constants of cyclization and hydrogen abstraction reactions using the density functional theory (DFT) method. The solvent effect of pure and mixed solvents on PBDF formation is illustrated successfully. The structure-related hydrogen donation ability for hydrogen abstraction controls the bias of competition reactions and influences PBDF formation. Water resulted to be the most significant generation of PBDFs. Fulvic and humic acid display higher hydrogen donation ability than small-molecule organics due to the partitioning effect in aqueous solution. Quantitative structure-activity relationship (QSAR) models of the calculated rate constants for 512 cyclization and 319 hydrogen abstraction reactions using 189 PBDEs as the initial reactants in water are established, revealing the high risk of PBDF formation in aqueous solution.

Theoretical Investigation on Hydrogen Abstraction Reactions of Sulfur Compounds HSX(O)H and CH3SX(O)H (X = C, S) by OH Radicals

The kinetic and mechanistic investigation of oxidation reactions of HSC(O)H, HSS(O)H, CH3SC(O)H, and CH3SS(O)H by OH radicals is performed extensively with the help of theoretical calculations. The potential energy profiles for the titled reactions are constructed at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ level. Two isomers, cis and trans, are observed for both HSC(O)H and HSS(O)H molecules. Reaction enthalpies and reaction Gibbs free energies are calculated employing the M06-2X/aug-cc-pVTZ method. The kinetic study uses canonical variational transition state theory and small-curvature tunneling in the temperature range of 210–350 K. CVT/SCT rate coefficients are utilized for calculating branching ratios. The atmospheric lifetime of HSC(O)H is computed to be 26.76 h, 3.51 h for HSS(O)H, 1.55 years for CH3SC(O)H, and 18.20 h for CH3SS(O)H. The global warming potential (GWP) and global temperature change potential (GTP) of CH3SC(O)H are found to be significant, while cis-HSC(O)H, trans-HSC(O)H, cis-HSS(O)H, trans-HSS(O)H, and CH3SS(O)H have negligible GWPs and GTPs.

Processing of hydroxylamine, NH2OH, an important prebiotic precursor, on interstellar ices

ABSTRACT Hydroxylamine, NH2OH, is one of the already detected interstellar molecules with the highest prebiotic potential. Yet, the abundance of this molecule found by astronomical observations is rather low for a relatively simple molecule, ∼10−10 relative to H2. This seemingly low abundance can be rationalized by destruction routes operating on interstellar dust grains. In this work, we tested the viability of this hypothesis under several prisms, finding that the origin of a lower abundance of NH2OH can be explained by two chemical processes, one operating at low temperature (10 K) and the other at intermediate temperature (20 K). At low temperatures, enabling the hydrogen abstraction reaction HNO + H → NO + H2, even in small amounts, partially inhibits the formation of NH2OH through successive hydrogenation of NO, and reduces its abundance on the grains. We found that enabling a 15–30 per cent of binding sites for this reaction results in reductions of NH2OH abundance of approximately one to two orders of magnitude. At warmer temperatures (20 K, in our study), the reaction NH2OH + H → HNOH + H2, which was found to be fast (k ∼ 106 s−1) in this work, followed by further abstractions by adsorbates that are immobile at 10 K (O, N) are the main route of NH2OH destruction. Our results shed light on the abundance of hydroxylamine in space and pave the way to constraining the subsequent chemistry experienced by this molecule and its derivatives in the interstellar prebiotic chemistry canvas.