Hygroscopic Properties of Internally Mixed Particles of Ammonium Sulfate and Succinic Acid Studied by Infrared Spectroscopy

2010 ◽  
Vol 114 (20) ◽  
pp. 6124-6130 ◽  
Author(s):  
Lorena Miñambres ◽  
María N. Sánchez ◽  
Fernando Castaño ◽  
Francisco J. Basterretxea
Keyword(s):  
Infrared Spectroscopy ◽  
Succinic Acid ◽  
Ammonium Sulfate ◽  
Hygroscopic Properties

scholarly journals Hygroscopic behavior of multicomponent organic aerosols and their internal mixtures with ammonium sulfate

2015 ◽  
Vol 15 (16) ◽  
pp. 23357-23405 ◽  
Author(s):  
B. Jing ◽  
S. R. Tong ◽  
Q. F. Liu ◽  
K. Li ◽  
W. G. Wang ◽  
...  
Keyword(s):  
Oxalic Acid ◽  
Succinic Acid ◽  
Ammonium Sulfate ◽  
Water Uptake ◽  
Malonic Acid ◽  
Phthalic Acid ◽  
Water Soluble ◽  
Organic Mixture ◽  
Hygroscopic Properties ◽  
Hygroscopic Behavior

Abstract. Water soluble organic compounds (WSOCs) are important components of organics in the atmospheric fine particulate matter. Although WSOCs play an important role in the hygroscopicity of aerosols, water uptake behavior of internally mixed WSOC aerosols remains limited characterization. Here, the hygroscopic properties of single component such as levoglucosan, oxalic acid, malonic acid, succinic acid and phthalic acid and multicomponent WSOC aerosols mainly involving oxalic acid are investigated with the hygroscopicity tandem differential mobility analyzer (HTDMA). The coexisting hygroscopic species including levoglucosan, malonic acid and phthalic acid have strong influence on the hygroscopic growth and phase behavior of oxalic acid, even suppress its crystallization completely. The interactions between oxalic acid and levoglucosan are confirmed by infrared spectra. The discrepancies between measured growth factors and predictions from Extended Aerosol Inorganics Model (E-AIM) with UNIFAC method and Zdanovskii–Stokes–Robinson (ZSR) approach increase at medium and high relative humidity (RH) assuming oxalic acid in a solid state. For the internal mixture of oxalic acid with levoglucosan or succinic acid, there is enhanced water uptake at high RH due to positive chemical interactions between solutes. Organic mixture has more complex effect on the hygroscopicity of ammonium sulfate than single species. Although hygroscopic species such as levoglucosan accounts for a small fraction in the multicomponent aerosols, they may still strongly influence the hygroscopic behavior of ammonium sulfate by changing phase state of oxalic acid which plays the role of "intermediate" species. Considering the abundance of oxalic acid in the atmospheric aerosols, its mixtures with hygroscopic species may significantly promote water uptake under high RH conditions and thus affect the cloud condensation nuclei (CCN) activity, optical properties and chemical reactivity of atmospheric particles.

scholarly journals Hygroscopic behavior of multicomponent organic aerosols and their internal mixtures with ammonium sulfate

2016 ◽  
Vol 16 (6) ◽  
pp. 4101-4118 ◽  
Author(s):  
Bo Jing ◽  
Shengrui Tong ◽  
Qifan Liu ◽  
Kun Li ◽  
Weigang Wang ◽  
...  
Keyword(s):  
Oxalic Acid ◽  
Succinic Acid ◽  
Ammonium Sulfate ◽  
Water Uptake ◽  
Malonic Acid ◽  
Phthalic Acid ◽  
Water Soluble ◽  
Organic Mixture ◽  
Hygroscopic Properties ◽  
Hygroscopic Behavior

Abstract. Water-soluble organic compounds (WSOCs) are important components of organics in the atmospheric fine particulate matter. Although WSOCs play an important role in the hygroscopicity of aerosols, knowledge on the water uptake behavior of internally mixed WSOC aerosols remains limited. Here, the hygroscopic properties of single components such as levoglucosan, oxalic acid, malonic acid, succinic acid, phthalic acid, and multicomponent WSOC aerosols mainly involving oxalic acid are investigated with the hygroscopicity tandem differential mobility analyzer (HTDMA). The coexisting hygroscopic species including levoglucosan, malonic acid, and phthalic acid have a strong influence on the hygroscopic growth and phase behavior of oxalic acid, even suppressing its crystallization completely during the drying process. The phase behaviors of oxalic acid/levoglucosan mixed particles are confirmed by infrared spectra. The discrepancies between measured growth factors and predictions from Extended Aerosol Inorganics Model (E-AIM) with the Universal Quasi-Chemical Functional Group Activity Coefficient (UNIFAC) method and Zdanovskii–Stokes–Robinson (ZSR) approach increase at medium and high relative humidity (RH) assuming oxalic acid in a crystalline solid state. For the internal mixture of oxalic acid with levoglucosan or succinic acid, there is enhanced water uptake at high RH compared to the model predictions based on reasonable oxalic acid phase assumption. Organic mixture has more complex effects on the hygroscopicity of ammonium sulfate than single species. Although hygroscopic species such as levoglucosan account for a small fraction in the multicomponent aerosols, they may still strongly influence the hygroscopic behavior of ammonium sulfate by changing the phase state of oxalic acid which plays the role of "intermediate" species. Considering the abundance of oxalic acid in the atmospheric aerosols, its mixtures with hygroscopic species may significantly promote water uptake under high RH conditions and thus affect the cloud condensation nuclei (CCN) activity, optical properties, and chemical reactivity of atmospheric particles.

scholarly journals Structure and Properties of Ln2MoO6 Oxymolybdates (Ln = La, Pr, Nd) Doped with Magnesium

Crystals ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 611
Author(s):  
Ekaterina Orlova ◽  
Elena Kharitonova ◽  
Timofei Sorokin ◽  
Alexander Antipin ◽  
Nataliya Novikova ◽  
...  
Keyword(s):  
Rare Earth ◽  
Infrared Spectroscopy ◽  
Room Temperature ◽  
High Temperature Phase ◽  
Temperature Phase ◽  
Spectroscopy Data ◽  
Structure And Properties ◽  
Hygroscopic Properties ◽  
Thermogravimetric Studies ◽  
Mg Doped

The literature data and the results obtained by the authors on the study of the structure and properties of a series of polycrystalline and single-crystal samples of pure and Mg-doped oxymolybdates Ln2MoO6 (Ln = La, Pr, Nd) are analyzed. Presumably, the high-temperature phase I41/acd of Nd2MoO6 single crystals is retained at room temperature. The reason for the loss of the center of symmetry in the structures of La2MoO6 and Pr2MoO6 and the transition to the space group I4¯c2 is the displacement of oxygen atoms along the twofold diagonal axes. In all structures, Mg cations are localized near the positions of the Mo atoms, and the splitting of the positions of the atoms of rare-earth elements is found. Thermogravimetric studies, as well as infrared spectroscopy data for hydrated samples of Ln2MoO6 (Ln = La, Pr, Nd), pure and with an impurity of Mg, confirm their hygroscopic properties.

scholarly journals Deliquescence, efflorescence, and phase miscibility of mixed particles of ammonium sulfate and isoprene-derived secondary organic material

2012 ◽  
Vol 12 (4) ◽  
pp. 9903-9943 ◽  
Author(s):  
M. L. Smith ◽  
A. K. Bertram ◽  
S. T. Martin
Keyword(s):  
Liquid Phase ◽  
Relative Humidity ◽  
Ammonium Sulfate ◽  
Organic Material ◽  
Important Variable ◽  
Oxidation Products ◽  
Liquid Separation ◽  
Inorganic Particles ◽  
Photo Oxidation ◽  
Hygroscopic Properties

Abstract. The hygroscopic phase transitions of ammonium sulfate mixed with isoprene-derived secondary organic material were investigated in aerosol experiments. The organic material was produced by isoprene photo-oxidation at 40% relative humidity. The low volatility fraction of the photo-oxidation products condensed onto ammonium sulfate particles. The particle-phase organic material had oxygen-to-carbon ratios of 0.67 to 0.74 for mass concentrations of 20 to 30 μg m−3. The deliquescence, efflorescence, and phase miscibility of the mixed particles were investigated using a dual arm tandem differential mobility analyzer. The isoprene photo-oxidation products induced deviations in behavior relative to pure ammonium sulfate. Compared to an efflorescence relative humidity (ERH) of 30 to 35% for pure ammonium sulfate, efflorescence was eliminated for mixed aqueous particles having organic volume fractions ε of approximately 0.6 and greater. Compared to a deliquescence relative humidity (DRH) of 80% for pure ammonium sulfate, the DRH steadily decreased for increasing ε, approaching a DRH of 40% for ε of 0.9. Parameterizations of the DRH(ε) and ERH(ε) curves were as follows: DRH(ε)= Σ i ci,d xi valid for 0 ≤ ε ≤ 0.86 and ERH(ε)= Σ i ci,e xi valid for 0 ≤ ε ≤ 0.55 for the coefficients c0,d= 80.67, c0,e = 28.35, c1,d= −11.45, c1,e = −13.66, c2,d = 0, c2,e = 0, c3,d = 57.99, c3,e = −83.80, c4,d = −106.80, and c4,d = 0. The molecular description that is thermodynamically implied by these strongly sloped DRH(ε) and ERH(ε) curves is that the organic isoprene photo-oxidation products, the inorganic ammonium sulfate, and water form a miscible liquid phase even at low relative humidity. This phase miscibility is in contrast to the liquid-liquid separation that occurs for some other types of secondary organic material. These differences in liquid-liquid separation are consistent with a prediction recently presented in the literature that the bifurcation between liquid-liquid phase separation versus mixing depends on the oxygen-to-carbon ratio of the organic material. The conclusions are that the influence of secondary organic material on the hygroscopic properties of ammonium sulfate varies with organic composition and that the degree of oxygenation of the organic material, which is a measurable characteristic of complex organic materials, is an important variable influencing the hygroscopic properties of mixed organic-inorganic particles.

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

2017 ◽  
Author(s):  
Xiaowei Wang ◽  
Bo Jing ◽  
Fang Tan ◽  
Jiabi Ma ◽  
Yunhong Zhang ◽  
...  
Keyword(s):  
Growth Factors ◽  
Chemical Composition ◽  
Relative Humidity ◽  
Oxalic Acid ◽  
Ammonium Sulfate ◽  
Water Uptake ◽  
Atmospheric Environment ◽  
Dehydration Process ◽  
Hygroscopic Properties ◽  
Ammonium Hydrogen

Abstract. Although water uptake of aerosols plays an important role in the atmospheric environment, the effects of interactions between components on chemical composition and hygroscopicity of aerosols 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 oxalic acid dihydrate at 77 % relative humidity (RH), and further lose crystalline water to convert into anhydrous oxalic acid 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 % RH, 44.3 ± 2.5 % RH 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 partial deliquescence relative humidity (DRH) for mixed OA/AS particles with OIR of 1:3 and 1:1 is observed to occur at 81.1 ± 1.5 % RH and 77 ± 1.0 % RH, respectively. The Raman spectra of mixed OA/AS droplets indicate the formation of ammonium hydrogen oxalate (NH4HC2O4) and ammonium hydrogen sulfate (NH4HSO4) from interactions between OA and AS in aerosols after slow dehydration process in 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 3:1 ratio exhibit no deliquescence transition over the RH range studied due to the considerable transformation of (NH4)2SO4 into nonhygroscopic NH4HC2O4. 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 NH4HC2O4 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.

Hygroscopic properties of the oxidation products of monoterpenes when condensing on ammonium sulfate aerosols

1998 ◽  
Vol 29 ◽  
pp. S5-S6 ◽  
Author(s):  
A. Virkkula ◽  
R. van Dingenen ◽  
F. Raes ◽  
J. Hjorth ◽  
N. Jensen ◽  
...  
Keyword(s):  
Ammonium Sulfate ◽  
Oxidation Products ◽  
Sulfate Aerosols ◽  
Hygroscopic Properties

Nano-HTDMA for investigating hygroscopic properties of sub-10 nm aerosol nanoparticles

2021 ◽  
Author(s):  
Ting Lei ◽  
Nan Ma ◽  
Juan Hong ◽  
Thomas Tuch ◽  
Xin Wang ◽  
...  
Keyword(s):  
Phase Transition ◽  
Ammonium Sulfate ◽  
Sodium Sulfate ◽  
Size Dependence ◽  
Current Knowledge ◽  
Measurement Techniques ◽  
Aerosol Flow ◽  
Aerosol Nanoparticles ◽  
Hygroscopic Properties ◽  
Inorganic Substances

<p>Interactions between water and nanoparticles are of great significance for atmospheric multiphase processes, physical chemistry, and materials science. Current knowledge of the hygroscopic and related physicochemical properties of nanoparticles, however, is insufficient due to limitations of the available measurement techniques. Here, we present the design and performance of a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA) apparatus. To enable high accuracy and precision in hygroscopicity measurements of sub-10 nm aerosol nanoparticles, systematic and comprehensive calibration criteria of nano-HTDMA have been developed and applied, including sheath/aerosol flow rates, DMA voltage, relative humidity (RH) sensor, temperature sensor, and particle sizing. After calibration, the nano-HTDMA system has been shown to have an accurate sizing and a small sizing offsets between the two DMAs (<1.4%) for aerosol nanoparticles with diameters down to 6 nm. Moreover, to maintain the RH-uniformities that prevent the pre-deliquescence and non-prompt phase transition of nanoparticles within DMA2, the RH of sheath flow is kept as same as that of aerosol flow at inlet of DMA2, and the humidification system and the DMA2 system are placed in a well-insulated and air conditioner housing (±0.1K). Using nano-HTDMA system. We investigate the hygroscopic behavior of aerosol nanoparticles of two inorganic substances (e.g., ammonium sulfate and sodium sulfate). A strong size dependence of the hygroscopic growth factor is observed for ammonium sulfate and sodium sulfate nanoparticles with diameters down to 6 nm, respectively. For size dependence of phase transition, we find a weak size dependence of DRH and ERH of ammonium sulfate nanoparticles with diameters from 6 to 100 nm but a pronounced size dependence of DRH and ERH between 20 and  6 nm for sodium sulfate nanoparticles.</p>

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