Piperazine Enhancing Sulfuric Acid-Based New Particle Formation: Implications for the Atmospheric Fate of Piperazine

Ma, Fangfang; Xie, Hong-Bin; Elm, Jonas; Shen, Jianjian; Chen, Jingwen; Vehkamäki, Hanna

doi:10.1021/acs.est.9b02117

Cited by 49 publications

(58 citation statements)

References 115 publications

(275 reference statements)

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“…Quantum chemistry calculations of PZ-H 2 SO 4 clusters suggest that the homogeneous nucleation process may even compete with PZ removal by OH radicals. 43 …”

Section: Discussionmentioning

confidence: 99%

Experimental and Theoretical Study of the OH-Initiated Degradation of Piperazine under Simulated Atmospheric Conditions

et al. 2020

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The OH-initiated photo-oxidation of piperazine and 1-nitropiperazine as well as the photolysis of 1-nitrosopiperazine were investigated in a large atmospheric simulation chamber. The rate coefficient for the reaction of piperazine with OH radicals was determined by the relative rate method to be k OH-piperazine = (2.8 ± 0.6) × 10 –10 cm 3 molecule –1 s –1 at 307 ± 2 K and 1014 ± 2 hPa. Product studies showed the piperazine + OH reaction to proceed both via C–H and N–H abstraction, resulting in the formation of 1,2,3,6-tetrahydropyrazine as the major product and in 1-nitropiperazine and 1-nitrosopiperazine as minor products. The branching in the piperazinyl radical reactions with NO, NO 2 , and O 2 was obtained from 1-nitrosopiperazine photolysis experiments and employed analyses of the 1-nitropiperazine and 1-nitrosopiperazine temporal profiles observed during piperazine photo-oxidation. The derived initial branching between N–H and C–H abstraction by OH radicals, k N–H /( k N–H + k C–H ), was 0.18 ± 0.04. All experiments were accompanied by substantial aerosol formation that was initiated by the reaction of piperazine with nitric acid. Both primary and secondary photo-oxidation products including 1-nitropiperazine and 1,4-dinitropiperazine were detected in the aerosol particles formed. Corroborating atmospheric photo-oxidation schemes for piperazine and 1-nitropiperazine were derived from M06-2X/aug-cc-pVTZ quantum chemistry calculations and master equation modeling of the pivotal reaction steps. The atmospheric chemistry of piperazine is evaluated, and a validated chemical mechanism for implementation in dispersion models is presented.

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“…Quantum chemistry calculations of PZ-H 2 SO 4 clusters suggest that the homogeneous nucleation process may even compete with PZ removal by OH radicals. 43 …”

Section: Discussionmentioning

confidence: 99%

Experimental and Theoretical Study of the OH-Initiated Degradation of Piperazine under Simulated Atmospheric Conditions

et al. 2020

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“…The global minimum structures of the pure (MEA)1-4 clusters were taken from our previous study. 11 A multi-step global minimum sampling scheme, which has been applied to study atmospheric cluster formation in previous studies, 11,[60][61][62][63] was employed to search for the global minima of the (MEA)m(MSA)n (m = 0-4, n = 1-4) clusters. The details for the scheme were presented in our previous study.…”

Section: Computational Detailsmentioning

confidence: 99%

“…The details for the scheme were presented in our previous study. 11,63 Briefly, around 10000 initial random configurations for each level and DLPNO-CCSD(T)/aug-cc-pVTZ level of theory were selected as the core optimization/frequency and single point energy calculation method, respectively, since they have shown good performance for studying the formation of atmospheric molecular cluster. [66][67][68][69][70] The Gibbs free energy for each global minima was calculated at mentioning that there are two reported global minima for cluster (MA)1(MSA)1.…”

Section: Computational Detailsmentioning

confidence: 99%

Methanesulfonic Acid-driven New Particle Formation Enhanced by Monoethanolamine: A Computational Study

Shen

Xie

Elm

et al. 2019

Environ. Sci. Technol.

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103

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Amines are recognized as significant enhancing species on methanesulfonic acid (MSA)-driven new particle formation (NPF). Monoethanolamine (MEA) has been detected in the atmosphere and its concentration could be significantly increased once MEA-based post-combustion CO2 capture technology is widely implemented. Here, we evaluated the enhancing potential of MEA on MSA-driven NPF by examining the formation of MEA-MSA clusters using a combination of quantum chemical calculations and kinetics modeling. The results indicate that-OH group of MEA can form at least one hydrogen bond with MSA or MEA in all MEA-containing clusters. The enhancing potential of MEA is higher than that of the strongest enhancing agent known so far, methylamine (MA), for MSA-driven NPF. Such high enhancing potential can be ascribed to not only the higher gas-phase basicity, but also the role of the additional-OH group of MEA in increasing the binding free energy by forming additional hydrogen bonds. This clarifies the importance of hydrogen-bonding capacity from the non-amino group of amines in enhancing MSA-driven NPF. The main growth pathway for MEA-MSA clusters proceeds via the initial formation of the (MEA)1(MSA)1 cluster, followed by alternately adding one MSA and one MEA molecule, differing from the case of MA-MSA clusters.

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“…Thermochemistry of clusters containing amm, dma, gua and tmao were taken from our previous studies (Myllys et al, 2018(Myllys et al, , 2019b(Myllys et al, , 2020. Thermochemistry of clusters with mea, put and pz were taken from a database , collected from original publications of Xie et al (2017), Elm et al (2017) and Ma et al (2019). Available structures with ma and tma were taken from Olenius et al (2017) and, to be consistent with the level of theory used, structures were optimized and frequencies calculated at the ωB97X-D/6-3 https://doi.org/10.5194/acp-2021-84 Preprint.…”

Section: Cluster Thermodynamicsmentioning

confidence: 99%

A Predictive Model for Salt Nanoparticle Formation UsingHeterodimer Stability Calculations

Barsanti¹,

Smith²,

Myllys³

2021

Preprint

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Abstract. Acid–base clusters and stable salt formation are critical drivers of new particle formation events in the atmosphere. In this study, we explore the relationship between J1.5, the theoretically predicted formation rate of clusters larger than 4 acid and 4 base molecules, and acid–base heterodimer stability, a property that is relatively easy to calculate using computational methods. Heterodimer stability as a function of gas-phase acidity, aqueous-phase acidity, heterodimer proton transference, vapor pressure, dipole moment, and polarizability were explored for the salts comprised of sulfuric acid, methanesulfonic acid, and nitric acid with nine bases. The best predictor of heterodimer stability was found to be gas-phase acidity. The relationship between heterodimer stability and J1.5 was analyzed for sulfuric acid salts over a range of monomer concentrations from 105 to 109 molec cm−3 and temperatures from 248 to 348 K. Heterodimer concentration was calculated from heterodimer stability and yielded an expression for predicting J1.5 for any salt, given approximately equal acid and base monomer concentrations and knowledge of monomer concentration and temperature. This parameterization was tested for the sulfuric acid–ammonia system by comparing the predicted values to experimental data and was found to be accurate within 2 orders of magnitude. We show that one can create a simple parameterization that incorporates the dependence on temperature and monomer concentration on J1.5 by defining a new term that we call the normalized heterodimer concentration, Φ. A plot of J1.5 vs. Φ collapses to a single monotonic curve for all weak salts of sulfuric acid, and can be used to accurately estimate J1.5 in atmospheric models.

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Piperazine Enhancing Sulfuric Acid-Based New Particle Formation: Implications for the Atmospheric Fate of Piperazine

Cited by 49 publications

References 115 publications

Experimental and Theoretical Study of the OH-Initiated Degradation of Piperazine under Simulated Atmospheric Conditions

Experimental and Theoretical Study of the OH-Initiated Degradation of Piperazine under Simulated Atmospheric Conditions

Methanesulfonic Acid-driven New Particle Formation Enhanced by Monoethanolamine: A Computational Study

A Predictive Model for Salt Nanoparticle Formation UsingHeterodimer Stability Calculations

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