scholarly journals Chemical ionization of clusters formed from sulfuric acid and dimethylamine or diamines

2016 ◽  
Author(s):  
Coty N. Jen ◽  
Jun Zhao ◽  
Peter H. McMurry ◽  
David R. Hanson
Keyword(s):  
Sulfuric Acid ◽  
Chemical Ionization ◽  
Flow Reactor ◽  
Cluster Formation ◽  
Mass Spectrometers ◽  
Model Calculations ◽  
Molecule Reaction ◽  
Base Content ◽  
Atmospheric Nucleation ◽  
High Base

Abstract. Chemical ionization (CI) mass spectrometers are used to study atmospheric nucleation by detecting clusters produced by reactions of sulfuric acid and various basic gases. These instruments typically use nitrate to deprotonate and thus chemically ionize the clusters. In this study, we compare cluster concentrations measured using either nitrate or acetate. Clusters were formed in a flow reactor from vapors of sulfuric acid and dimethylamine, ethylene diamine, tetramethylethylene diamine, or butanediamine (also known as putrescine). These comparisons show that nitrate is unable to chemically ionize clusters with high base content. In addition, we vary the ion-molecule reaction time to probe ion processes which include proton-transfer, ion-molecule clustering, and decomposition of ions. Ion decomposition upon deprotonation by acetate/nitrate was observed. More studies are needed to quantify to what extent ion decomposition affects observed cluster content and concentrations, especially those chemically ionized with acetate since it deprotonates more types of clusters than nitrate. Model calculations of the neutral and ion cluster formation pathways are also presented to better identify the cluster types that are not efficiently deprotonated by nitrate. Comparison of model and measured clusters indicate that sulfuric acid dimer with two diamines and sulfuric acid trimer with two or more base molecules are not efficiently chemical ionized by nitrate. We conclude that acetate CI provides better information on cluster abundancies and their base content than nitrate CI.

scholarly journals Chemical ionization of clusters formed from sulfuric acid and dimethylamine or diamines

2016 ◽  
Vol 16 (19) ◽  
pp. 12513-12529 ◽  
Author(s):  
Coty N. Jen ◽  
Jun Zhao ◽  
Peter H. McMurry ◽  
David R. Hanson
Keyword(s):  
Sulfuric Acid ◽  
Reaction Time ◽  
Chemical Ionization ◽  
Flow Reactor ◽  
Cluster Formation ◽  
Mass Spectrometers ◽  
Molecule Reaction ◽  
Base Content ◽  
Atmospheric Nucleation ◽  
High Base

Abstract. Chemical ionization (CI) mass spectrometers are used to study atmospheric nucleation by detecting clusters produced by reactions of sulfuric acid and various basic gases. These instruments typically use nitrate to deprotonate and thus chemically ionize the clusters. In this study, we compare cluster concentrations measured using either nitrate or acetate. Clusters were formed in a flow reactor from vapors of sulfuric acid and dimethylamine, ethylene diamine, tetramethylethylene diamine, or butanediamine (also known as putrescine). These comparisons show that nitrate is unable to chemically ionize clusters with high base content. In addition, we vary the ion–molecule reaction time to probe ion processes which include proton-transfer, ion–molecule clustering, and decomposition of ions. Ion decomposition upon deprotonation by acetate/nitrate was observed. More studies are needed to quantify to what extent ion decomposition affects observed cluster content and concentrations, especially those chemically ionized with acetate since it deprotonates more types of clusters than nitrate.Model calculations of the neutral and ion cluster formation pathways are also presented to better identify the cluster types that are not efficiently deprotonated by nitrate. Comparison of model and measured clusters indicate that sulfuric acid dimers with two diamines and sulfuric acid trimers with two or more base molecules are not efficiently chemical ionized by nitrate. We conclude that acetate CI provides better information on cluster abundancies and their base content than nitrate CI.

scholarly journals The charging of neutral dimethylamine and dimethylamine–sulfuric acid clusters using protonated acetone

2015 ◽  
Vol 8 (6) ◽  
pp. 2577-2588
Author(s):  
K. Ruusuvuori ◽  
P. Hietala ◽  
O. Kupiainen-Määttä ◽  
T. Jokinen ◽  
H. Junninen ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Chemical Ionization ◽  
Lower Troposphere ◽  
Particle Formation ◽  
Atmospheric Conditions ◽  
Atmospheric Particle ◽  
Organic Bases ◽  
Atmospheric Nucleation ◽  
Quantum Chemical Methods ◽  
Vapour Concentration

Abstract. Sulfuric acid is generally considered one of the most important substances taking part in atmospheric particle formation. However, in typical atmospheric conditions in the lower troposphere, sulfuric acid and water alone are unable to form particles. It has been suggested that strong bases may stabilize sulfuric acid clusters so that particle formation may occur. More to the point, amines – strong organic bases – have become the subject of interest as possible cause for such stabilization. To probe whether amines play a role in atmospheric nucleation, we need to be able to measure accurately the gas-phase amine vapour concentration. Such measurements often include charging the neutral molecules and molecular clusters in the sample. Since amines are bases, the charging process should introduce a positive charge. This can be achieved by, for example, using chemical ionization with a positively charged reagent with a suitable proton affinity. In our study, we have used quantum chemical methods combined with a cluster dynamics code to study the use of acetone as a reagent ion in chemical ionization and compared the results with measurements performed with a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (CI-APi-TOF). The computational results indicate that protonated acetone is an effective reagent in chemical ionization. However, in the experiments the reagent ions were not depleted at the predicted dimethylamine concentrations, indicating that either the modelling scheme or the experimental results – or both – contain unidentified sources of error.

scholarly journals Measurement of iodine species and sulfuric acid using bromide chemical ionization mass spectrometers

2020 ◽  
Author(s):  
Mingyi Wang ◽  
Xu-Cheng He ◽  
Henning Finkenzeller ◽  
Siddharth Iyer ◽  
Dexian Chen ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Chemical Ionization ◽  
Detection Limits ◽  
Particle Formation ◽  
Cloud Chamber ◽  
Ionization Mass ◽  
New Particle Formation ◽  
Reduced Pressure ◽  
Mass Spectrometers ◽  
Iodine Species

Abstract. Iodine species are important in the marine atmosphere for oxidation and new-particle formation. Understanding iodine chemistry and iodine new-particle formation requires high time resolution, high sensitivity, and simultaneous measurements of many iodine species. Here, we describe the application of bromide chemical ionization mass spectrometers (Br-CIMS) to this task. During iodine new-particle formation experiments in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber, we have measured gas-phase iodine species and sulfuric acid using two Br-CIMS, one coupled to a Multi-scheme chemical IONization inlet (Br-MION-CIMS) and the other to a Filter Inlet for Gasses and AEROsols inlet (Br-FIGAERO-CIMS). From offline calibrations and inter-comparisons with other instruments attached to the CLOUD chamber, we have quantified the sensitivities of the Br-MION-CIMS to HOI, I2, and H2SO4 and obtain detection limits of 5.8 × 106, 6.3 × 105, and 2.0 × 105 molec cm−3, respectively, for a 2-min integration time. From binding energy calculations, we estimate the detection limit for HIO3 to be 1.2 × 105 molec cm−3, based on an assumption of maximum sensitivity. Detection limits in the Br-FIGAERO-CIMS are around one order of magnitude higher than those in the Br-MION-CIMS; for example, the detection limits for HOI and HIO3 are 3.3 × 107 and 5.1 × 106 molec cm−3, respectively. Our comparisons of the performance of the MION inlet and the FIGAERO inlet show that bromide chemical ionization mass spectrometers using either atmospheric pressure or reduced pressure interfaces are well-matched to measuring iodine species and sulfuric acid in marine environments.

scholarly journals Measurement of iodine species and sulfuric acid using bromide chemical ionization mass spectrometers

2021 ◽  
Vol 14 (6) ◽  
pp. 4187-4202
Author(s):  
Mingyi Wang ◽  
Xu-Cheng He ◽  
Henning Finkenzeller ◽  
Siddharth Iyer ◽  
Dexian Chen ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Chemical Ionization ◽  
Detection Limits ◽  
Particle Formation ◽  
High Time Resolution ◽  
Ionization Mass ◽  
New Particle Formation ◽  
Reduced Pressure ◽  
Mass Spectrometers ◽  
Iodine Species

Abstract. Iodine species are important in the marine atmosphere for oxidation and new-particle formation. Understanding iodine chemistry and iodine new-particle formation requires high time resolution, high sensitivity, and simultaneous measurements of many iodine species. Here, we describe the application of a bromide chemical ionization mass spectrometer (Br-CIMS) to this task. During the iodine oxidation experiments in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber, we have measured gas-phase iodine species and sulfuric acid using two Br-CIMS, one coupled to a Multi-scheme chemical IONization inlet (Br-MION-CIMS) and the other to a Filter Inlet for Gasses and AEROsols inlet (Br-FIGAERO-CIMS). From offline calibrations and intercomparisons with other instruments, we have quantified the sensitivities of the Br-MION-CIMS to HOI, I2, and H2SO4 and obtained detection limits of 5.8 × 106, 3.8 × 105, and 2.0 × 105 molec. cm−3, respectively, for a 2 min integration time. From binding energy calculations, we estimate the detection limit for HIO3 to be 1.2 × 105 molec. cm−3, based on an assumption of maximum sensitivity. Detection limits in the Br-FIGAERO-CIMS are around 1 order of magnitude higher than those in the Br-MION-CIMS; for example, the detection limits for HOI and HIO3 are 3.3 × 107 and 5.1 × 106 molec. cm−3, respectively. Our comparisons of the performance of the MION inlet and the FIGAERO inlet show that bromide chemical ionization mass spectrometers using either atmospheric pressure or reduced pressure interfaces are well-matched to measuring iodine species and sulfuric acid in marine environments.

scholarly journals Sulfuric acid nucleation: power dependencies, variation with relative humidity, and effect of bases

2012 ◽  
Vol 12 (10) ◽  
pp. 4399-4411 ◽  
Author(s):  
J. H. Zollner ◽  
W. A. Glasoe ◽  
B. Panta ◽  
K. K. Carlson ◽  
P. H. McMurry ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Flow Reactor ◽  
Sulfuric Acid Concentration ◽  
Particle Growth ◽  
Ionization Mass ◽  
Particle Detection ◽  
Nitrogen Base ◽  
Condensation Particle Counter ◽  
Atmospheric Nucleation ◽  
New Treatment

Abstract. Nucleation of particles composed of sulfuric acid, water, and nitrogen base molecules was studied using a continuous flow reactor. The particles formed from these vapors were detected with an ultrafine condensation particle counter, while vapors of sulfuric acid and nitrogen bases were detected by chemical ionization mass spectrometry. Variation of particle numbers with sulfuric acid concentration yielded a power dependency on sulfuric acid of 5 ± 1 for relative humidities of 14–68% at 296 K; similar experiments with varying water content yielded power dependencies on H2O of ~7. The critical cluster contains about 5 H2SO4 molecules and a new treatment of the power dependency for H2O suggests about 12 H2O molecules for these conditions. Addition of 2-to-45 pptv of ammonia or methyl amine resulted in up to millions of times more particles than in the absence of these compounds. Particle detection capabilities, sulfuric acid and nitrogen base detection, wall losses, and the extent of particle growth are discussed. Results are compared to previous laboratory nucleation studies and they are also discussed in terms of atmospheric nucleation scenarios.

scholarly journals Sulfuric acid nucleation: power dependencies, variation with relative humidity, and effect of bases

2012 ◽  
Vol 12 (1) ◽  
pp. 1117-1150 ◽  
Author(s):  
J. H. Zollner ◽  
W. A. Glasoe ◽  
B. Panta ◽  
K. K. Carlson ◽  
P. H. McMurry ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Flow Reactor ◽  
Sulfuric Acid Concentration ◽  
Particle Growth ◽  
Ionization Mass ◽  
Particle Detection ◽  
Nitrogen Base ◽  
Condensation Particle Counter ◽  
Atmospheric Nucleation ◽  
New Treatment

Abstract. Nucleation of particles composed of sulfuric acid, water, and nitrogen base molecules was studied using a continuous flow reactor. The particles formed from these vapors were detected with an ultrafine condensation particle counter, while vapors of sulfuric acid and nitrogen bases were detected by chemical ionization mass spectrometry. Variation of particle numbers with sulfuric acid concentration yielded a power dependency on sulfuric acid of 5 ± 1 for relative humidities of 14–68% at 296 K; similar experiments with varying water content yielded power dependencies on H2O of ~7. The critical cluster contains about 5 H2SO4 molecules and a new treatment of the power dependency for H2O suggests about 12 H2O molecules for these conditions. Addition of 2-to-45 pptv of ammonia or methyl amine resulted in up to millions of times more particles than in the absence of these compounds. Particle detection efficiencies, sulfuric acid and nitrogen base detection, wall losses, and the extent of particle growth are discussed with the help of a recent computational fluid dynamics study that simulated the flow and chemistry in the flow reactor. Results are compared to previous laboratory nucleation studies and they are also discussed in terms of atmospheric nucleation scenarios.

scholarly journals A method for detecting the presence of organic fraction in nucleation mode sized particles

2005 ◽  
Vol 5 (12) ◽  
pp. 3277-3287 ◽  
Author(s):  
P. Vaattovaara ◽  
M. Räsänen ◽  
T. Kühn ◽  
J. Joutsensaari ◽  
A. Laaksonen
Keyword(s):  
Sulfuric Acid ◽  
Field Experiments ◽  
Inorganic Compounds ◽  
Particle Diameter ◽  
Ethanol Vapor ◽  
Organic Fraction ◽  
Saturation Ratio ◽  
Nucleation Mode ◽  
Atmospheric Nucleation ◽  
20 Nm

Abstract. New particle formation and growth has a very important role in many climate processes. However, the overall knowlegde of the chemical composition of atmospheric nucleation mode (particle diameter, d<20 nm) and the lower end of Aitken mode particles (d≤50 nm) is still insufficient. In this work, we have applied the UFO-TDMA (ultrafine organic tandem differential mobility analyzer) method to shed light on the presence of an organic fraction in the nucleation mode size class in different atmospheric environments. The basic principle of the organic fraction detection is based on our laboratory UFO-TDMA measurements with organic and inorganic compounds. Our laboratory measurements indicate that the usefulness of the UFO-TDMA in the field experiments would arise especially from the fact that atmospherically the most relevant inorganic compounds do not grow in subsaturated ethanol vapor, when particle size is 10 nm in diameter and saturation ratio is about 86% or below it. Furthermore, internally mixed particles composed of ammonium bisulfate and sulfuric acid with sulfuric acid mass fraction ≤33% show no growth at 85% saturation ratio. In contrast, 10 nm particles composed of various oxidized organic compounds of atmospheric relevance are able to grow in those conditions. These discoveries indicate that it is possible to detect the presence of organics in atmospheric nucleation mode sized particles using the UFO-TDMA method. In the future, the UFO-TDMA is expected to be an important aid to describe the composition of atmospheric newly-formed particles.

A free jet flow reactor for ion/molecule reaction studies at very low energies

1990 ◽  
Vol 97 (1) ◽  
pp. 55-86 ◽  
Author(s):  
M. Hawley ◽  
T.L. Mazely ◽  
L.K. Randeniya ◽  
R.S. Smith ◽  
X.K. Zeng ◽  
...  
Keyword(s):  
Flow Reactor ◽  
Jet Flow ◽  
Free Jet ◽  
Molecule Reaction ◽  
Low Energies ◽  
Free Jet Flow

scholarly journals A Monte Carlo approach for determining cluster evaporation rates from concentration measurements

2016 ◽  
Author(s):  
Oona Kupiainen-Määttä
Keyword(s):  
Experimental Data ◽  
Monte Carlo ◽  
Markov Chain ◽  
Sulfuric Acid ◽  
Markov Chain Monte Carlo ◽  
Mass Spectrometer ◽  
Large Fraction ◽  
Cluster Formation ◽  
Unknown Parameters ◽  
Ammonia Clusters

Abstract. Evaporation rates of small negatively charged sulfuric acid–ammonia clusters are determined by combining detailed cluster formation simulations with cluster distributions measured at CLOUD. The analysis is performed by varying the evaporation rates with Markov chain Monte Carlo (MCMC), running cluster formation simulations with each new set of evaporation rates and comparing the obtained cluster distributions to the measurements. In a second set of simulations, the fragmentation of clusters in the mass spectrometer due to energetic collisions is studied by treating also the fragmentation probabilities as unknown parameters and varying them with MCMC. This second set of simulations results in a better fit to the experimental data, suggesting that a large fraction of the observed HSO4− and HSO4− ⋅ H2SO4 signals may result from fragmentation of larger clusters, most importantly the HSO4− ⋅ (H2SO4)2 trimer.

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