Hygroscopic properties of oxalic acid and atmospherically relevant oxalates

Ma, Qingxia; He, Hong; Liu, Chang

doi:10.1016/j.atmosenv.2012.12.011

Cited by 49 publications

(55 citation statements)

References 48 publications

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“…While our measurements for the pure mono-valent chloride aerosols (with no oxalate) yield κ values that are consistent with previously measured values, measurements for mono-valent salts containing oxalate are similar to those of salt-hydrates, even after drying. This is consistent with the findings of Ma et al (2013), which suggest the persistence of hydrates under dry conditions, without heating in addition to drying. Addition of oxalate to sodium (mono-valent) dominated salt particles has only a modest effect, due to their high solubility.…”

Section: Resultssupporting

confidence: 82%

“…(Table 3). As for the mono-valent salts, this is reasonable because fully removing water from the deliquesced salt particles can require heating in addition to low humidity (Ma et al, 2013). …”

Section: Resultsmentioning

confidence: 99%

“…Studies of both pure components of salt/DCA particles (e.g., CaCO 3 , H 2 C 2 O 4 , CaC 2 O 4 ) as well as external mixtures of particles of these pure components indicate that dust or salt particles that include DCA may show reduced hygroscopicities due to formation of low-solubility compounds (Sullivan et al, 2009;Ma et al, 2010Ma et al, , 2013Ma and He, 2012). While pure particles of DCA and salts and their external mixtures shed insight on the probable behavior of particles containing these compounds, internal mixtures of these components (single particles containing DCA, their organic salts, and inorganic salts) will also be important in the atmosphere.…”

Section: G Drozd Et Al: Inorganic Salts Interact With Organic Di-acidsmentioning

confidence: 99%

“…The ubiquity of di-carboxylic acids (DCA) is well documented both in urban and rural terrestrial aerosol and marine aerosol (Warneck, 2003;Tan et al, 2010;Sempéré and Kawamura, 1996;Pavuluri et al, 2010;Ma et al, 2013;Kundu et al, 2010;Kawamura et al, 1996Kawamura et al, , 2007Gierlus et al, 2012;Altieri et al, 2008). A recent study of marine aerosol from around the globe found that DCA contribute on average ∼ 15 % to total marine organic aerosol (OA) mass (Fu et al, 2013;Myriokefalitakis et al, 2011).…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultssupporting

confidence: 82%

Section: Resultsmentioning

confidence: 99%

Section: G Drozd Et Al: Inorganic Salts Interact With Organic Di-acidsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2014

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“…Previous studies have focused on deliquescence behavior of pure OA (Peng et al, 2001;Braban et al, 2003;Miñambres et al, 2013;Ma et al, 2013a;Jing et al, 2016). It was found that due to its high deliquescence point, OA exhibited no deliquescence transition or hygroscopic growth within the relative humidity (RH) range studied by an electrodynamic balance (EDB) (Peng et al, 2001), vapor sorption analyzer (Ma et al, 2013a) or hygroscopicity tandem differential mobility analyzer (HTDMA) (Jing et al, 2016).…”

Section: Introductionmentioning

confidence: 99%

Hygroscopic behavior and chemical composition evolution of internally mixed aerosols composed of oxalic acid and ammonium sulfate

et al. 2017

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Abstract. Although water uptake of aerosol particles plays an important role in the atmospheric environment, the effects of interactions between components on chemical composition and hygroscopicity of particles are still not well constrained. The hygroscopic properties and phase transformation of oxalic acid (OA) and mixed particles composed of ammonium sulfate (AS) and OA with different organic to inorganic molar ratios (OIRs) have been investigated by using confocal Raman spectroscopy. It is found that OA droplets first crystallize to form OA dihydrate at 71 % relative humidity (RH), and further lose crystalline water to convert into anhydrous OA around 5 % RH during the dehydration process. The deliquescence and efflorescence point for AS is determined to be 80.1 ± 1.5 % RH and 44.3 ± 2.5 % RH, respectively. The observed efflorescence relative humidity (ERH) for mixed OA / AS droplets with OIRs of 1 : 3, 1 : 1 and 3 : 1 is 34.4 ± 2.0, 44.3 ± 2.5 and 64.4 ± 3.0 % RH, respectively, indicating the elevated OA content appears to favor the crystallization of mixed systems at higher RH. However, the deliquescence relative humidity (DRH) of AS in mixed OA / AS particles with OIRs of 1 : 3 and 1 : 1 is observed to occur at 81.1 ± 1.5 and 77 ± 1.0 % RH, respectively. The Raman spectra of mixed OA / AS droplets indicate the formation of ammonium hydrogen oxalate (NH 4 HC 2 O 4 ) and ammonium hydrogen sulfate (NH 4 HSO 4 ) from interactions between OA and AS in aerosols during the dehydration process on the time scale of hours, which considerably influence the subsequent deliquescence behavior of internally mixed particles with different OIRs. The mixed OA / AS particles with an OIR of 3 : 1 exhibit no deliquescence transition over the RH range studied due to the considerable transformation of (NH 4 ) 2 SO 4 into NH 4 HC 2 O 4 with a high DRH. Although the hygroscopic growth of mixed OA / AS droplets is comparable to that of AS or OA at high RH during the dehydration process, Raman growth factors of mixed particles after deliquescence are substantially lower than those of mixed OA / AS droplets during the efflorescence process and further decrease with elevated OA content. The discrepancies for Raman growth factors of mixed OA / AS particles between the dehydration and hydration process at high RH can be attributed to the significant formation of NH 4 HC 2 O 4 and residual OA, which remain solid at high RH and thus result in less water uptake of mixed particles. These findings improve the understanding of the role of reactions between dicarboxylic acid and inorganic salt in the chemical and physical properties of aerosol particles, and might have important implications for atmospheric chemistry.

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Effect of Water on the Structure and Stability of Hydrogen‐Bonded Oxalic Acid Dimer

Zhang

et al. 2017

ChemPhysChem

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As the simplest and most abundant dicarboxylic acid in the atmosphere, oxalic acid (OA) not only plays a key role in aerosol nucleation, but also acts as a prototypical compound for the investigation of intra- and intermolecular hydrogen-bonding interactions. A systematic theoretical study on the hydrated OA dimers performed by using DFT at the M06-2X/6-311++G(3df, 2p) level is discussed herein. The properties of hydrogen bonds in clusters are inspected through topological analysis by using atoms in molecules (AIM) theory. The most stable OA dimer involves a cyclic structure with two intermolecular hydrogen bonds. Calculations show that one H O has a slight effect on the hydrogen bonds, whereas two water molecules weaken and three water molecules break the two intermolecular hydrogen bonds between OAs. Furthermore, there are no hydrogen-bond interactions between OAs in almost all stable clusters as the number of H O molecules increases to four and five. Additionally, ionization and isomerization of OA through water-assisted proton-transfer phenomena are observed in tetra- and pentahydrates. This work provides new insights into the conversion of anhydrous OA into hydrated clusters that are helpful for further understanding the atmospheric nucleation process and nature of hydrogen bond.

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Hygroscopic properties of oxalic acid and atmospherically relevant oxalates

Cited by 49 publications

References 48 publications

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

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

Hygroscopic behavior and chemical composition evolution of internally mixed aerosols composed of oxalic acid and ammonium sulfate

Effect of Water on the Structure and Stability of Hydrogen‐Bonded Oxalic Acid Dimer

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