Experimental studies of the ion-induced binary nucleation

Singh, J. J.; Smith, A. C.; Yue, Glenn K.

doi:10.1016/0021-8502(82)90031-3

Cited by 7 publications

(3 citation statements)

References 13 publications

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“…The possibility of redox reactions from sulfate to sulfite was ignored because these have not been observed in mass spectrometric studies even though sulfuric acid has been widely investigated by these methods. [49][50][51][52][53] Because the same mass signal could have various assignments, we studied the peak behaviour as a function of the SO 4 2À /Al 3+ ratio.…”

Section: àmentioning

confidence: 99%

Identification of hydrolysis products of AlCl₃·6H₂O in the presence of sulfate by electrospray ionizationtime-of-flight mass spectrometry and computational methods

Sarpola

Saukkoriipi

Hietapelto

et al. 2007

Phys. Chem. Chem. Phys.

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ElectroSpray Ionization-Mass Spectrometry (ESI-MS) and computational methods (DFT, MP2, and COSMO) were used to investigate the hydrolysis products of aluminium chloride as a function of sulfate concentration at pH 3.7. With the aid of computational chemistry, structural information was deduced from the chemical compositions observed with ESI-MS. Many novel types of hydrolysis products were noted, revealing that our present understanding of aluminium speciation is too simple. The role of counterions was found to be critical: the speciation of aluminium changed markedly as a function of sulfate concentration. Ab initio calculations were used to reveal the energetically most favoured structures of aluminium sulfate anions and cations selected from the ESI-MS results. Several interesting observations were made. Most importantly, the bonding behaviour of the sulfate group changed as the number of aqua ligands increased. The accompanying structural rearrangement of the clusters revealed the highly active role of sulfate as a ligand. The gas phase calculations were expanded to the aquatic environment using a conductor-like screening model. As expected, the bonding behaviour of the sulfate group in the minimum energy structures was distinctly different in the aquatic environment compared to the gas phase. Together, these methods open a new window for research in the solution chemistry of aluminium species.

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Section: àmentioning

confidence: 99%

Identification of hydrolysis products of AlCl₃·6H₂O in the presence of sulfate by electrospray ionizationtime-of-flight mass spectrometry and computational methods

Sarpola

Saukkoriipi

Hietapelto

et al. 2007

Phys. Chem. Chem. Phys.

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“…The protonated water clusters were one of the first systems to be investigated, and equilibrium measurements of Δ G °, Δ H °, and Δ S ° for the stepwise association of H 2 O ligands to form the H + (H 2 O) w series have been performed by a number of research groups. ,,− Thermodynamic parameters for hundreds of cluster ion reactions have now been characterized using both equilibrium and nonequilibrium experimental methods . The H + (H 2 SO 4 ) s (H 2 O) w cluster ions were first identified in the laboratory for s ≤ 6 by Singh et al using mass spectrometry. Sharp and Futrell later observed the H + (H 2 SO 4 ) s (H 2 O) w series up through s = 20 using fast atom bombardment of sulfuric acid solutions.…”

Section: Introductionmentioning

confidence: 99%

“…8,9,[11][12][13][14][15] Thermodynamic parameters for hundreds of cluster ion reactions have now been characterized using both equilibrium and nonequilibrium experimental methods. 3 The H + (H 2 SO 4 ) s (H 2 O) w cluster ions were first identified in the laboratory for s e 6 by Singh et al 16 using mass spectrometry. Sharp and Futrell 17 later observed the H + (H 2 SO 4 ) s (H 2 O) w series up through s ) 20 using fast atom bombardment of sulfuric acid solutions.…”

Section: Introductionmentioning

confidence: 99%

Experimental Thermodynamics of Cluster Ions Composed of H₂SO₄ and H₂O. 1. Positive Ions

Froyd

Lovejoy

2003

J. Phys. Chem. A

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Predictions from gas phase nucleation models are highly sensitive to the thermodynamics of the initial stages of particle growth, where free energies calculated using classical nucleation theory are expected to be the least accurate. There is strong evidence that H 2 SO 4 and H 2 O are directly involved in atmospheric nucleation. These species are also principal components of atmospheric ions, suggesting that they may play important roles in ion-induced nucleation mechanisms. In part 1 of this work, we measured equilibrium constants for the reactions of H 2 O with the cluster ions, H + (H 2 SO 4 ) s (H 2 O) w , s e 4 and w e 15, over a range of temperatures using an ion flow reactor. H 2 O bond enthalpies and entropies were derived from van't Hoff analyses, and results for the H + (H 2 O) w system are in agreement with literature values. Thermodynamics of H 2 SO 4 binding in the H + (H 2 SO 4 ) s (H 2 O) w cluster ions were also estimated based on comparisons with the HSO 4 -(H 2 SO 4 ) s system, whose bond enthalpies were measured previously. As clusters grow in size, some thermodynamic trends begin to reflect those for bulk H 2 SO 4 /H 2 O solutions. A stable population of the H + (H 2 O) w cluster ions is present in the atmosphere, but for typical concentrations, incorporation of the first H 2 SO 4 molecule to form H + (H 2 SO 4 )(H 2 O) w is thermodynamically unfavorable at 270 K. As a result, significant growth and subsequent nucleation of the H + (H 2 SO 4 ) s (H 2 O) w system is not anticipated in the middle or lower troposphere.

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Tropospheric Aerosol Formation: Processes, Observations and Simulations

Turco

2000

Chemistry and Radiation Changes in the Ozone Layer

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Experimental studies of the ion-induced binary nucleation

Cited by 7 publications

References 13 publications

Identification of hydrolysis products of AlCl₃·6H₂O in the presence of sulfate by electrospray ionizationtime-of-flight mass spectrometry and computational methods

Identification of hydrolysis products of AlCl₃·6H₂O in the presence of sulfate by electrospray ionizationtime-of-flight mass spectrometry and computational methods

Experimental Thermodynamics of Cluster Ions Composed of H₂SO₄ and H₂O. 1. Positive Ions

Tropospheric Aerosol Formation: Processes, Observations and Simulations

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Experimental studies of the ion-induced binary nucleation

Cited by 7 publications

References 13 publications

Identification of hydrolysis products of AlCl3·6H2O in the presence of sulfate by electrospray ionizationtime-of-flight mass spectrometry and computational methods

Identification of hydrolysis products of AlCl3·6H2O in the presence of sulfate by electrospray ionizationtime-of-flight mass spectrometry and computational methods

Experimental Thermodynamics of Cluster Ions Composed of H2SO4 and H2O. 1. Positive Ions

Tropospheric Aerosol Formation: Processes, Observations and Simulations

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Identification of hydrolysis products of AlCl₃·6H₂O in the presence of sulfate by electrospray ionizationtime-of-flight mass spectrometry and computational methods

Identification of hydrolysis products of AlCl₃·6H₂O in the presence of sulfate by electrospray ionizationtime-of-flight mass spectrometry and computational methods

Experimental Thermodynamics of Cluster Ions Composed of H₂SO₄ and H₂O. 1. Positive Ions