scholarly journals Molecular corridors and parameterizations of volatility in the evolution of organic aerosols

2015 ◽  
Vol 15 (19) ◽  
pp. 27877-27915
Author(s):  
Y. Li ◽  
U. Pöschl ◽  
M. Shiraiwa
Keyword(s):  
Organic Compounds ◽  
Molar Mass ◽  
High Resolution Mass Spectrometry ◽  
Measurement Data ◽  
Organic Aerosols ◽  
Indoor Environments ◽  
High Molar Mass ◽  
High Volatility ◽  
Sulfur Containing ◽  
Sulfur Containing Compounds

Abstract. The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the volatility of organic compounds containing oxygen, nitrogen and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less oxidized indoor OA are constrained to a corridor of low molar mass and high volatility, whereas highly oxygenated compounds in atmospheric water extend to high molar mass and low volatility. Among the nitrogen- and sulfur-containing compounds identified in atmospheric aerosols, amines tend to exhibit low molar mass and high volatility, whereas organonitrates and organosulfates follow high O : C corridors extending to high molar mass and low volatility. We suggest that the consideration of molar mass and molecular corridors can help to constrain volatility and particle phase state in the modeling of OA particularly for nitrogen- and sulfur-containing compounds.

scholarly journals Molecular corridors and parameterizations of volatility in the chemical evolution of organic aerosols

2016 ◽  
Vol 16 (5) ◽  
pp. 3327-3344 ◽  
Author(s):  
Ying Li ◽  
Ulrich Pöschl ◽  
Manabu Shiraiwa
Keyword(s):  
Organic Compounds ◽  
Molar Mass ◽  
High Resolution Mass Spectrometry ◽  
Measurement Data ◽  
Organic Aerosols ◽  
Indoor Environments ◽  
High Molar Mass ◽  
High Volatility ◽  
Sulfur Containing ◽  
Sulfur Containing Compounds

Abstract. The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the saturation mass concentration of organic compounds containing oxygen, nitrogen, and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less-oxidized indoor OA are constrained to a corridor of low molar mass and high volatility, whereas highly oxygenated compounds in atmospheric water extend to high molar mass and low volatility. Among the nitrogen- and sulfur-containing compounds identified in atmospheric aerosols, amines tend to exhibit low molar mass and high volatility, whereas organonitrates and organosulfates follow high O : C corridors extending to high molar mass and low volatility. We suggest that the consideration of molar mass and molecular corridors can help to constrain volatility and particle-phase state in the modeling of OA particularly for nitrogen- and sulfur-containing compounds.

Considerations for the physical vapor deposition of high molar mass organic compounds

Vacuum ◽  
2014 ◽  
Vol 109 ◽  
pp. 26-33 ◽  
Author(s):  
Jeffrey S. Castrucci ◽  
Jeremy D. Dang ◽  
Brett A. Kamino ◽  
Andrew Campbell ◽  
David Pitts ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Vapor Deposition ◽  
Physical Vapor Deposition ◽  
Molar Mass ◽  
High Molar Mass

scholarly journals Predictions of the glass transition temperature and viscosity of organic aerosols from volatility distributions

2020 ◽  
Vol 20 (13) ◽  
pp. 8103-8122 ◽  
Author(s):  
Ying Li ◽  
Douglas A. Day ◽  
Harald Stark ◽  
Jose L. Jimenez ◽  
Manabu Shiraiwa
Keyword(s):  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Organic Compounds ◽  
Transport Model ◽  
Organic Aerosols ◽  
Chemical Transport ◽  
Basis Set ◽  
Southeastern Us ◽  
Sulfur Containing

Abstract. Volatility and viscosity are important properties of organic aerosols (OA), affecting aerosol processes such as formation, evolution, and partitioning of OA. Volatility distributions of ambient OA particles have often been measured, while viscosity measurements are scarce. We have previously developed a method to estimate the glass transition temperature (Tg) of an organic compound containing carbon, hydrogen, and oxygen. Based on analysis of over 2400 organic compounds including oxygenated organic compounds, as well as nitrogen- and sulfur-containing organic compounds, we extend this method to include nitrogen- and sulfur-containing compounds based on elemental composition. In addition, parameterizations are developed to predict Tg as a function of volatility and the atomic oxygen-to-carbon ratio based on a negative correlation between Tg and volatility. This prediction method of Tg is applied to ambient observations of volatility distributions at 11 field sites. The predicted Tg values of OA under dry conditions vary mainly from 290 to 339 K and the predicted viscosities are consistent with the results of ambient particle-phase-state measurements in the southeastern US and the Amazonian rain forest. Reducing the uncertainties in measured volatility distributions would improve predictions of viscosity, especially at low relative humidity. We also predict the Tg of OA components identified via positive matrix factorization of aerosol mass spectrometer (AMS) data. The predicted viscosity of oxidized OA is consistent with previously reported viscosity of secondary organic aerosols (SOA) derived from α-pinene, toluene, isoprene epoxydiol (IEPOX), and diesel fuel. Comparison of the predicted viscosity based on the observed volatility distributions with the viscosity simulated by a chemical transport model implies that missing low volatility compounds in a global model can lead to underestimation of OA viscosity at some sites. The relation between volatility and viscosity can be applied in the molecular corridor or volatility basis set approaches to improve OA simulations in chemical transport models by consideration of effects of particle viscosity in OA formation and evolution.

scholarly journals Predictions of the glass transition temperature and viscosity of organic aerosols by volatility distributions

2020 ◽  
Author(s):  
Ying Li ◽  
Douglas A. Day ◽  
Harald Stark ◽  
Jose Jimenez ◽  
Manabu Shiraiwa
Keyword(s):  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Organic Compounds ◽  
Organic Aerosols ◽  
Chemical Transport ◽  
Basis Set ◽  
Southeastern Us ◽  
Spectrometer Data ◽  
Sulfur Containing

Abstract. Volatility and viscosity are important properties of organic aerosols (OA), affecting aerosol processes such as formation, evolution and partitioning of OA. Volatility distributions of ambient OA particles have often been measured, while viscosity measurements are scarce. We have previously developed a method to estimate glass transition temperature (Tg) of an organic compound containing carbon, hydrogen, and oxygen. Based on analysis of over 2300 organic compounds including oxygenated organic compounds as well as nitrogen- and sulfur-containing organic compounds, we extend this method to include nitrogen- and sulfur-containing compounds based on elemental composition. In addition, parameterizations are developed to predict Tg as a function of volatility and the atomic oxygen-to-carbon ratio based on a negative correlation between Tg and volatility. The prediction method of Tg and viscosity is applied to ambient observations of volatility distributions at eleven field sites. The predicted Tg varies mainly from 290 K to 339 K and the predicted viscosities are consistent with the results of ambient particle phase state measurements in the southeastern US and the Amazonian rain forest. Reducing the uncertainties in measured volatility distributions would be helpful to improve predictions of viscosity especially at low relative humidity. We also predict the Tg of OA components identified via positive matrix factorization of aerosol mass spectrometer data. The predicted viscosity of oxidized OA is consistent with previously reported viscosity of SOA derived from α-pinene, toluene, isoprene epoxydiol (IEPOX), and of diesel fuel. Comparison of the predicted viscosity based on the observed volatility distributions with the viscosity simulated by a chemical transport model implies that missing low volatility compounds in a global model can lead to underestimation of OA viscosity at some sites. The relation between volatility and viscosity can be applied in the molecular corridor or volatility basis set approaches to improve OA simulations in chemical transport models by consideration of effects of particle viscosity in OA formation and evolution.

Paper Chemistry: Interactions of thermo mechanical pulp fractions with high molar mass cationic polyacrylamides: Part 2. Flocculation

2010 ◽  
Vol 25 (3) ◽  
pp. 310-318 ◽  
Author(s):  
Tero Taipale ◽  
Janne Laine ◽  
Susanna Holappa ◽  
Jonni Ahlgren ◽  
Juan Cecchini
Keyword(s):  
Molar Mass ◽  
High Molar Mass ◽  
Mechanical Pulp ◽  
Paper Chemistry

scholarly journals Highly Efficient MOF Catalyst Systems for CO2 Conversion to Bis-Cyclic Carbonates as Building Blocks for NIPHUs (Non-Isocyanate Polyhydroxyurethanes) Synthesis

Catalysts ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 628
Author(s):  
Adolfo Benedito ◽  
Eider Acarreta ◽  
Enrique Giménez
Keyword(s):  
Molar Mass ◽  
Cycloaddition Reaction ◽  
Building Blocks ◽  
Catalyst System ◽  
Cyclic Carbonate ◽  
Ammonium Bromide ◽  
Cyclic Carbonates ◽  
High Molar Mass ◽  
Highly Efficient ◽  
Free Process

The present paper describes a greener sustainable route toward the synthesis of NIPHUs. We report a highly efficient solvent-free process to produce [4,4′-bi(1,3-dioxolane)]-2,2′-dione (BDC), involving CO2, as renewable feedstock, and bis-epoxide (1,3-butadiendiepoxide) using only metal–organic frameworks (MOFs) as catalysts and cetyltrimethyl-ammonium bromide (CTAB) as a co-catalyst. This synthetic procedure is evaluated in the context of reducing global emissions of waste CO2 and converting CO2 into useful chemical feedstocks. The reaction was carried out in a pressurized reactor at pressures of 30 bars and controlled temperatures of around 120–130 °C. This study examines how reaction parameters such as catalyst used, temperature, or reaction time can influence the molar mass, yield, or reactivity of BDC. High BDC reactivity is essential for producing high molar mass linear non-isocyanate polyhydroxyurethane (NIPHU) via melt-phase polyaddition with aliphatic diamines. The optimized Al-OH-fumarate catalyst system described in this paper exhibited a 78% GC-MS conversion for the desired cyclic carbonates, in the absence of a solvent and a 50 wt % chemically fixed CO2. The cycloaddition reaction could also be carried out in the absence of CTAB, although lower cyclic carbonate yields were observed.

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