Sink or Surf: Atmospheric Implications for Succinic Acid at Aqueous Surfaces

Blower, Patrick G.; Ota, Stephanie T.; Valley, Nicholas A.; Wood, Suzannah R.; Richmond, Geraldine L.

doi:10.1021/jp405067y

Cited by 24 publications

(55 citation statements)

References 102 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, considering the constant ratio, no significant changes in orientation over the studied concentration range are anticipated. In recent publications by Blower et al 34 and Ruehl et al, 35 where the orientation of succinic acid at the aqueous interface was investigated, supplemental evidence can be found. Their final analysis led to the conclusion that succinic acid in aqueous solution mainly orients with the carboxylic acid groups on the same side of the molecule when looking along its CH 2 -CH 2 -axis, which was also found by Roberts et al.…”

Section: Probing the Surface With Xps: Succinic Acid At Different Promentioning

confidence: 99%

Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension

Werner

Julin

Dalirian

et al. 2014

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

PostprintThis is the accepted version of a paper published in Physical Chemistry, Chemical Physics -PCCP. This paper has been peer-reviewed but does not include the final publisher proof-corrections or journal pagination.Citation for the original published paper (version of record):Werner, J., Julin, J., Dalirian, M., Prisle, N., Ohrwall, G. et al. (2014) Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension. The water-vapor interface of aqueous solutions of succinic acid, where pH value and bulk concentration were varied, has been studied using surface sensitive X-ray photoelectron spectroscopy (XPS) and molecular dynamics (MD) simulations. It was found that succinic acid has a considerably higher propensity to reside in the aqueous surface region than its deprotonated form, which is effectively depleted from the surface due to the two strongly hydrated carboxylate groups. From both XPS experiments and MD simulations a strongly increased concentration of the acid form in the surface region compared to the bulk concentration was found and quantified. Detailed analysis of the surface of succinic acid solutions at different bulk concentrations led to the conclusion that succinic acid saturates the aqueous surface at high bulk concentrations. With the aid of MD simulations the thickness of the surface layer could be estimated, which enabled the quantification of surface concentration of succinic acid as multiple of the known bulk concentration. The obtained enrichment factors were successfully used to model surface tension of these binary aqueous solutions using two different models that account for surface enrichment. This underlines the close correlation of increased concentration at the surface relative to the bulk and reduced surface tension of aqueous solutions of succinic acid. The results of this study shed light on the microscopic origin of surface tension, a macroscopic property. Furthermore, the impact of the results from this study on atmospheric modeling is discussed.

show abstract

Section: Probing the Surface With Xps: Succinic Acid At Different Promentioning

confidence: 99%

Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension

Werner

Julin

Dalirian

et al. 2014

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…NPF involves two distinct steps, i.e., nucleation to form a critical nucleus and subsequent growth of newly formed nanoparticles to a larger size (> 3 nm). Currently, the identities and the roles of chemical species involved in NPF are not fully understood at the molecular level, hindering the development of physically based parameterization to include NPF in atmospheric models (Zhang, 2010;Cai and Jiang, 2017). Sulfuric acid (SA) is believed to be the most common atmospheric nu-8004 Y.…”

Section: Introductionmentioning

confidence: 99%

Interaction between succinic acid and sulfuric acid–base clusters

Lin

et al. 2019

Atmos. Chem. Phys.

View full text Add to dashboard Cite

Abstract. Dicarboxylic acids likely participate in the formation of pre-nucleation clusters to facilitate new particle formation in the atmosphere, but the detailed mechanism leading to the formation of multicomponent critical nuclei involving organic acids, sulfuric acid (SA), base species, and water remains unclear. In this study, theoretical calculations are performed to elucidate the interactions between succinic acid (SUA) and clusters consisting of SA-ammonia (AM)∕dimethylamine (DMA) in the presence of hydration of up to six water molecules. Formation of the hydrated SUA⚫SA⚫ base clusters is energetically favorable, triggering proton transfer from SA to the base molecule to form new covalent bonds or strengthening the preexisting covalent bonds. The presence of SUA promotes hydration of the SA⚫AM and SA⚫AM⚫DMA clusters but dehydration of the SA⚫DMA clusters. At equilibrium, SUA competes with the second SA molecule for addition to the SA⚫ base clusters at atmospherically relevant concentrations. The clusters containing both the base and organic acid are capable of further binding with acid molecules to promote subsequent growth. Our results indicate that the multicomponent nucleation involving organic acids, sulfuric acid, and base species promotes new particle formation in the atmosphere, particularly under polluted conditions with a high concentration of diverse organic acids.

show abstract

“…In particular, the kinetics and energetics of acid dissociation at the air-water interface are expected to be significantly different than those in bulk water since the intermolecular forces experienced are fundamentally different in interfacial environments than in bulk environments. [5][6][7] For example, both experimental and computational studies have shown that the dissociation energetics and kinetics of HNO 3 change significantly at the water surface. 5,8,9 More specifically, X-ray photoelectron spectroscopy has shown that the degree of dissociation of HNO 3 decreases by B20% at the water surface relative to in bulk water.…”

Section: Introductionmentioning

confidence: 99%

Molecular dynamics simulations predict an accelerated dissociation of H₂CO₃at the air–water interface

Galib

Hanna

2014

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

The dissociation and decomposition reactions of carbonic acid (H2CO3) in bulk water have been thoroughly studied, but little is known about its reactivity at the air-water interface. Herein, we investigate the dissociation reaction of H2CO3 at the air-water interface using ab initio molecular dynamics and metadynamics. Our results indicate that H2CO3 (pKa = 3.45) dissociates faster at the water surface than in bulk water, in contrast to recent experiments and simulations which have shown that HNO3 (pKa = -1.3) has a lower propensity to dissociate at the water surface than in bulk water. We find that the water surface allows for a more structured solvation environment around H2CO3 than in bulk water, which contributes to a decrease in the dissociation energy barrier via a stabilization of the transition state relative to the undissociated acid. Given its decreased kinetic stability at the air-water interface, H2CO3 may play an important role in the acidification of atmospheric aerosols and water droplets.

show abstract

Sink or Surf: Atmospheric Implications for Succinic Acid at Aqueous Surfaces

Cited by 24 publications

References 102 publications

Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension

Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension

Interaction between succinic acid and sulfuric acid–base clusters

Molecular dynamics simulations predict an accelerated dissociation of H₂CO₃at the air–water interface

Contact Info

Product

Resources

About

Sink or Surf: Atmospheric Implications for Succinic Acid at Aqueous Surfaces

Cited by 24 publications

References 102 publications

Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension

Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension

Interaction between succinic acid and sulfuric acid–base clusters

Molecular dynamics simulations predict an accelerated dissociation of H2CO3at the air–water interface

Contact Info

Product

Resources

About

Molecular dynamics simulations predict an accelerated dissociation of H₂CO₃at the air–water interface