Determination of Evaporation Rates and Vapor Pressures of Very Low Volatility Compounds:  A Study of the C4−C10 and C12 Dicarboxylic Acids

Cappa, C. D.; Lovejoy, Edward R.; Ravishankara, A. R.

doi:10.1021/jp068686q

Cited by 96 publications

(183 citation statements)

References 56 publications

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“…The best-fit H v (C * ) for the two-product model was a constant H v = 72 kJ mol −1 . These values encompass the range of H v values for individual compounds found in POA (Bilde et al 2003;Cappa et al 2007;Epstein et al 2010). For example, C * values of high molecular weight n-alkanes, which are found in diesel exhaust, range from 61.5 kJ mol −1 for n-dodecane (C * ∼ 10 6 TABLE 1 Volatility distributions and H v (C * ) for the basis set and two-product model fits presented here, and the basis set fit from Grieshop et al (2009a) Grieshop et al (2009 This study (basis set) This study (two product) µg m −3 ) (Majer and Svoboda 1985) to 80.8 kJ mol −1 for neicosane (C * ∼ 10 3 µg m −3 ) (Chirico et al 1989) and 99.3 kJ mol −1 for n-octacosane (C * ∼ 10 1 µg m −3 ) (Chirico et al 1989).…”

Section: Fits To Absorptive Partitioning Theorymentioning

confidence: 95%

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Temperature Dependence of Gas–Particle Partitioning of Primary Organic Aerosol Emissions from a Small Diesel Engine

Ranjan

Presto

May

et al. 2012

Aerosol Science and Technology

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A new experimental technique has been developed to study the gas-particle partitioning behavior of primary organic aerosol (POA) emissions from combustion sources at atmospherically relevant concentrations. The technique involves slowly filling a Teflon chamber with a constant emission source. As aerosol concentrations increase inside the chamber, the gas-particle partitioning of semivolatile organics shifts to the particle phase, thus increasing the fuel-based POA emission factor. The technique allows characterization of partitioning under isothermal conditions and atmospherically relevant concentrations. The technique was evaluated using emissions from a small diesel engine; the measured changes in gas-particle partitioning agreed well with previously published data for this engine measured with a dilution sampler. The temperature dependence of the gas-particle partitioning was investigated by conducting experiments at three different temperatures (15• C, 26• C, and 33 • C). Increasing organic aerosol concentration and decreasing temperature increased the fuel-based POA emission factor. The gas-particle partitioning data were fit using absorptive partitioning theory to determine the volatility distribution and enthalpy of vaporization ( H v ) of the emissions. We have derived two fits; one using the volatility basis set approach and a second using a two-product model. Both fits are suitable for use in chemical transport models. These fits were tested using previously published thermodenuder data. Partitioning calculations predict that the gas-particle partitioning from POA emissions from this engine vary by about a factor of 4 across the atmospherically relevant range of temperature and organic aerosol concentrations. This underscores the semivolatile nature of POA emissions.

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Section: Fits To Absorptive Partitioning Theorymentioning

confidence: 95%

“…Individual organic compounds found in POA have H v of 100 kJ mol −1 or higher (Bilde et al 2003;Cappa et al 2007;Epstein et al 2010). However, experimental studies of SOA report much less temperature sensitivity, with effective H v values of ∼30 kJ mol −1 (Offenburg et al 2006;Pathak et al 2007;Stanier et al 2007).…”

Section: Introductionmentioning

confidence: 99%

Temperature Dependence of Gas–Particle Partitioning of Primary Organic Aerosol Emissions from a Small Diesel Engine

Ranjan

Presto

May

et al. 2012

Aerosol Science and Technology

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“…All of the TPD aerosol-CIMS experiments were performed at relative humidities below 10 % in order to keep the contribution of water negligible (Saleh et al, 2010;Cappa et al, 2007). This was done by drying the particles using silica gel dryer after particle generation.…”

Section: Temperature Programmed Desorption Aerosol-cimsmentioning

confidence: 99%

Inorganic salts interact with oxalic acid in submicron particles to form material with low hygroscopicity and volatility

et al. 2014

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Abstract. Volatility and hygroscopicity are two key properties of organic aerosol components, and both are strongly related to chemical identity. While the hygroscopicities of pure salts, di-carboxylic acids (DCA), and DCA salts are known, the hygroscopicity of internal mixtures of these components, as they are typically found in the atmosphere, has not been fully characterized. Here we show that inorganicorganic component interactions typically not considered in atmospheric models can lead to very strongly bound metalorganic complexes and greatly affect aerosol volatility and hygroscopicity; in particular, the bi-dentate binding of DCA to soluble inorganic ions. We have studied the volatility of pure, dry organic salt particles and the hygroscopicity of internal mixtures of oxalic acid (OxA, the dominant DCA in the atmosphere) and a number of salts, both mono-and divalent. The formation of very low volatility organic salts was confirmed, with minimal evaporation of oxalate salt particles below 75 • C. Dramatic increases in the cloud condensation nuclei (CCN) activation diameter for particles with di-valent salts (e.g., CaCl 2 ) and relatively small particle volume fractions of OxA indicate that standard volume additivity rules for hygroscopicity do not apply. Thus small organic compounds with high O : C ratios are capable of forming lowvolatility and very low hygroscopicity particles. Given current knowledge of the formation mechanisms of OxA and M-Ox salts, surface enrichment of insoluble M-Ox salts is expected. The resulting formation of an insoluble coating of metal-oxalate salts can explain low-particle hygroscopicities. The formation of particles with a hard coating could offer an alternative explanation for observations of glass-like particles without the need for a phase transition.

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“…They originate from photo-oxidation of biogenic and anthropogenic compounds but there is speculation about the exact origins and formation mechanisms. These vapour pressures have been previously studied by evaporation rates in Tandem Differential Mobility Analysers (TDMA) (Tao and McMurry, 1989;Bilde et al, 2003;Bilde and Pandis, 2001), Temperature Programmed Desorption (TPD) combined with Proton Transfer Chemical Ionisation Mass Spectrometry (PT-CIMS) (Cappa et al, 2007;Chattopadhyay and Ziemann, 2005), and Knudsen mass loss effusion (Silva et al, 2001(Silva et al, , 1999 and white light resonance spectroscopy (Zardini et al, 2006) and there are discrepancies between different measurement methods of up to two orders of magnitude for some compounds.…”

Section: Introductionmentioning

confidence: 99%

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Markus²,

et al. 2009

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Abstract.A design of and initial results from a Knudsen Effusion Mass Spectrometer (KEMS) are presented. The design was adapted from high temperature alloy studies with a view to using it to measure vapour pressures for low volatility organics. The system uses a temperature controlled cell with an effusive orifice. This produces a molecular beam which is sampled by a quadropole mass spectrometer with electron impact ionization calibrated to a known vapour pressure. We have determined P (298 K) and H sub of the first 5 saturated straight chain dicarboxylic acids: 2.15±1.19×10 −2 Pa and 75±19 KJ mol −1 respectively for oxalic acid, 5.73±1.14×10 −4 Pa and 91±4 KJ mol −1 for Malonic acid, 1.13±0.47×10 −4 Pa and 93±6 KJ mol −1 for Succinic acid, 4.21±1.66×10 −4 Pa and 123±22 KJ mol −1 for Glutaric acid and 6.09±3.85×10 −6 Pa and 125±40 KJ mol −1 for Adipic acid.

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Determination of Evaporation Rates and Vapor Pressures of Very Low Volatility Compounds: A Study of the C₄−C₁₀ and C₁₂ Dicarboxylic Acids

Cited by 96 publications

References 56 publications

Temperature Dependence of Gas–Particle Partitioning of Primary Organic Aerosol Emissions from a Small Diesel Engine

Temperature Dependence of Gas–Particle Partitioning of Primary Organic Aerosol Emissions from a Small Diesel Engine

Inorganic salts interact with oxalic acid in submicron particles to form material with low hygroscopicity and volatility

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

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