Surface tensions of solutions containing dicarboxylic acid mixtures

Lee, Jae Young; Hildemann, Lynn M.

doi:10.1016/j.atmosenv.2014.02.049

Cited by 17 publications

(11 citation statements)

References 31 publications

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“…These parametrizations come from several independent measurements 47 – 51 but we use the parameters of the Szyszkowski equation for each that are summarized in Lee and Hildemann. 49 In addition, we show results from the AFM approach only for a w close to the saturation limit, which is closest to our measured concentrations. Overall, our experimental results agree very well with bulk measurements.…”

Section: Resultssupporting

confidence: 85%

Precise, contactless measurements of the surface tension of picolitre aerosol droplets

et al. 2016

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Section: Resultssupporting

confidence: 85%

Precise, contactless measurements of the surface tension of picolitre aerosol droplets

et al. 2016

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“…In both cases, the underlying parameters (a 1 and b 2 ) for both fits to the macroscopic solution data (provided in SI Appendix, Table S2) agree with those given by Zdziennicka et al (54) for the Szyszkowski-Langmuir equation within reported uncertainties for the limiting case of binary water-Triton X-100 solution (i.e., primary solute concentration = 0 M). At the limit of a water-glutaric acid solution (i.e., surfactant concentration = 0 mM), a 1 and b 2 agree with literature values (56). At the limit of a water-NaCl solution, the fit function predicts a linear dependence of surface tension on salt concentration with the resulting coefficient a 2 b 1 slightly below literature values (57).…”

Section: Methodssupporting

confidence: 80%

The surface tension of surfactant-containing, finite volume droplets

Bzdek

Reid

Malila

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

110

119

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Surface tension influences the fraction of atmospheric particles that become cloud droplets. Although surfactants are an important component of aerosol mass, the surface tension of activating aerosol particles is still unresolved, with most climate models assuming activating particles have a surface tension equal to that of water. By studying picoliter droplet coalescence, we demonstrate that surfactants can significantly reduce the surface tension of finite-sized droplets below the value for water, consistent with recent field measurements. Significantly, this surface tension reduction is droplet size-dependent and does not correspond exactly to the macroscopic solution value. A fully independent monolayer partitioning model confirms the observed finite-size-dependent surface tension arises from the high surface-to-volume ratio in finite-sized droplets and enables predictions of aerosol hygroscopic growth. This model, constrained by the laboratory measurements, is consistent with a reduction in critical supersaturation for activation, potentially substantially increasing cloud droplet number concentration and modifying radiative cooling relative to current estimates assuming a water surface tension. The results highlight the need for improved constraints on the identities, properties, and concentrations of atmospheric aerosol surfactants in multiple environments and are broadly applicable to any discipline where finite volume effects are operative, such as studies of the competition between reaction rates within the bulk and at the surface of confined volumes and explorations of the influence of surfactants on dried particle morphology from spray driers.

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“…56,67 Instead, the reaction with other (primary and secondary) RO 2 • favorably (k ≈ 10 9 M −1 s −1 ) produces corresponding alcohols, carbonyls, and alkoxy radicals 56 that would proceed β-scission to emit neutral CH 3 − C(O)• radical 68 and the observed ketone at m/z = 155 (Scheme 2). We consider the m/z = 155 species as an important intermediate that may lead to the formation of 3-methyl-1,2,3butanetricarboxylic acid (MBTCA) 14,17,[31][32][33][34]69 as shown in Scheme 3. 15,18,69−72 A carboxylic acid group −C(O)OH formation during the reactions would occur via the acyl peroxyl radical + HO 2 •/RO 2 • reaction.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Because the hydrophobic character of CPA drives them to the surface of aqueous media such as fog and cloud droplets, as demonstrated by molecular dynamics (MD) calculation and surface-tension data, − it is critical to investigate the oxidation of aqueous CPA by ·OH(g) at the air–water interface. ,,− The MD study reveals that all 144 CPA molecules are partitioned to the surface (thickness ≤1 nm) of a 2000 water molecules droplet with the carbonyl and carboxylic groups pointing to the bulk phase . Thus, the oxidation of aqueous CPA by ·OH(g) is necessarily interfacial and may be different from that of gas or liquid phase. , We recently found surface-active C ≥4 dicarboxylic acids (DCAs) − react with gas phase ·OH-radical via an air–water interface specific mechanism . The products from the reactions HOOC–R n –COO – ( n = 2–6) + ·OH always include ( n – 1) products, that is, OC(H)–R n –1 –COO – and HOOC–R n –1 –COO – , implying that α-CH 2 groups of undissociated terminal HOOC moieties residing at the topmost layers of the water surfaces would react selectively with interfacial ·OH, followed by conversion into alkoxy −C–O· radicals that split HOCO· radical .…”

Section: Introductionmentioning

confidence: 99%

OH-Radical Oxidation of Surface-Active cis-Pinonic Acid at the Air–Water Interface

Enami

Sakamoto

2016

J. Phys. Chem. A

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Gaseous biogenic volatile organic compounds (BVOCs) are immediately oxidized by gaseous oxidants to form BVOC-acids that rapidly condense onto aqueous aerosol phase and thus contribute to the growth of atmospheric particles. Because BVOC-acids are highly hydrophobic and hence surface-active in nature, it seems critical to study the oxidation by gaseous hydroxyl radical (·OH(g)) at the air-water interface. Here we report on the fast (≤10 μs) oxidation of aqueous cis-pinonic acid (C10H16O3, CPA, cis-pinonate anion's m/z = 183), a representative BVOC-acid, by ·OH(g) at the air-water interface for the first time. We find that cis-pinonate anion is more enriched at the air-water interface by ∼4 and ∼14 times than n-octanoate anion at 10 and 100 μM, respectively, as revealed by an interface-specific mass spectrometry of the equimolar mixture of microjets. Exposure of aqueous CPA microjets to ·OH(g) pulses from the 266 nm laser photolysis of O3(g)/O2(g)/H2O(g)/N2(g) mixtures yields pinonic peroxyl radicals (m/z = 214) that lead to the functionalization products carbonyls (m/z = 197), alcohols (m/z = 199), and pinonic hydroperoxides (m/z = 215) in addition to smaller-mass products including carbonyls (m/z = 155 and 157). We confirmed the formation of the corresponding alcohols, aldehydes, and hydroperoxides in experiments performed in D2O solvent. The analysis of total mass balance implies a significant amount (>70%) of products would be emitted into the gas-phase during the heterogeneous ·OH-oxidations. Our results suggest ·OH-oxidations of amphiphilic BVOC-acids at the air-water interface may play a far more significant role in photochemical aging process of aqueous aerosols than previously assumed.

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Surface tensions of solutions containing dicarboxylic acid mixtures

Cited by 17 publications

References 31 publications

Precise, contactless measurements of the surface tension of picolitre aerosol droplets

Precise, contactless measurements of the surface tension of picolitre aerosol droplets

The surface tension of surfactant-containing, finite volume droplets

OH-Radical Oxidation of Surface-Active cis-Pinonic Acid at the Air–Water Interface

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