The thermodynamics of binary liquid mixtures : formic acid and water

Campbell, A. N.; Campbell, Alexandra Jean Robson

doi:10.1039/tf9343001109

Cited by 20 publications

(8 citation statements)

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“…For convenience, equations were fitted to the numbers he used. The form of these equations was determined by the relation -aRT = B (9) where B is the second virial coefficient; the form for B is indicated in the discussion by Beattie and Stockmayer (4). Applying the resulting form of equation for the a's to the numerical values given by Coolidge led to the result:…”

Section: B P-v-t Behavior Of the Vapormentioning

confidence: 99%

Some Thermodynamic Properties of Formic Acid.

Waring¹

1952

Chem. Rev.

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Section: B P-v-t Behavior Of the Vapormentioning

confidence: 99%

Some Thermodynamic Properties of Formic Acid.

Waring¹

1952

Chem. Rev.

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“…In fact, it is expected that the acid percentage in the vapors of solutions with low acid concentrations is equally low. In particular, the percentage of FA in the vapors of liquid solutions with 0.02 M of acid is expected approximately ≈2 % [16] . As results, the mass spectra are simplified, pure (FA) n or mixed (FA) m (H 2 O) n clusters are not formed, but the Na−FA(H 2 O) n are detected as low intensity peaks.…”

Section: Resultsmentioning

confidence: 82%

“…In particular, the percentage of FA in the vapors of liquid solutions with 0.02 M of acid is expected approximately ≈2 %. [16] As results, the mass spectra are simplified, pure (FA) n or mixed (FA) m (H 2 O) n clusters are not formed, but the Na−FA(H 2 O) n are detected as low intensity peaks. Nevertheless, it was still possible to evaluate the appearance energy of these clusters although with a signal/noise ratio lower than that of Na−(FA) n or Na−(H 2 O) n clusters.…”

Section: Resultsmentioning

confidence: 83%

Photoionization, Structures, and Energetics of Na‐Doped Formic Acid–Water Clusters

Palma¹,

Gaele²,

Bende³

2022

ChemPhysChem

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The influence of formic acid on water cluster aggregation has been investigated experimentally by mass spectrometry and tunable UV laser ionization applied to Na‐doped clusters formed in the supersonic expansion of water vapors seeded with formic acid (FA) as well as theoretically using high level quantum chemistry methods. The mass spectra of Na−FA(H2O)n clusters show an enlarging of mass distribution toward heavier clusters with respect to the Na−(H2O)n clusters, suggesting similar mass distribution in neutral clusters and an influence of formic acid in water aggregation. Density functional theory and coupled‐cluster type (DLPNO‐CCSD(T)) calculations have been used to calculate structures and energetics of neutral and ionized Na−FA(H2O)n as well as neutral FA(H2O)n. Na‐doped clusters are characterized by very stable geometries. The theoretical adiabatic ionization potential values match pretty well the measured appearance energies and the calculated first six electronic excited states show Rydberg‐type characters, indicating possible autoionization contributions in the mass spectra. Finally, theoretical calculations on neutral FA(H2O)n clusters show the possibility of similarly stable structures in small clusters containing up to n=4–5 water molecules, where FA interacts significantly with waters. This suggests that FA can compete with water molecules in the starting stage of the aggregation process, by forming stable nucleation seed.

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“…The total pressure of the system was calculated according to the additivity of the partial pressures P normalt normalo normalt normala normall = P normalH normalC normalO normalO normalH + P normalH 2 normalO / [ P a ] where P HCOOH and P H 2 O are the partial pressures of HCOOH and H 2 O, respectively. The results were compared with the experimentally measured total pressures of the HCOOH/H 2 O mixture at 291.15 and 303.15 K , without NaCl added. The HCOOH vapor mole fraction was calculated by y normalH normalC normalO normalO normalH = P normalH normalC normalO normalO normalH P normalt normalo normalt normala normall …”

Section: Methodsmentioning

confidence: 99%

Solubility of CO₂ in Aqueous Formic Acid Solutions and the Effect of NaCl Addition: A Molecular Simulation Study

et al. 2022

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There is a growing interest in the development of routes to produce formic acid from CO2, such as the electrochemical reduction of CO2 to formic acid. The solubility of CO2 in the electrolyte influences the production rate of formic acid. Here, the dependence of the CO2 solubility in aqueous HCOOH solutions with electrolytes on the composition and the NaCl concentration was studied by Continuous Fractional Component Monte Carlo simulations at 298.15 K and 1 bar. The chemical potentials of CO2, H2O, and HCOOH were obtained directly from single simulations, enabling the calculation of Henry coefficients and subsequently considering salting in or salting out effects. As the force fields for HCOOH and H2O may not be compatible due to the presence of strong hydrogen bonds, the Gibbs–Duhem integration test was used to test this compatibility. The combination of the OPLS/AA force field with a new set of parameters, in combination with the SPC/E force field for water, was selected. It was found that the solubility of CO2 decreases with increasing NaCl concentration in the solution and increases with the increase of HCOOH concentration. This continues up to a certain concentration of HCOOH in the solution, after which the CO2 solubility is high and the NaCl concentration has no significant effect.

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The thermodynamics of binary liquid mixtures : formic acid and water

Cited by 20 publications

References 0 publications

Some Thermodynamic Properties of Formic Acid.

Some Thermodynamic Properties of Formic Acid.

Photoionization, Structures, and Energetics of Na‐Doped Formic Acid–Water Clusters

Solubility of CO₂ in Aqueous Formic Acid Solutions and the Effect of NaCl Addition: A Molecular Simulation Study

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The thermodynamics of binary liquid mixtures : formic acid and water

Cited by 20 publications

References 0 publications

Some Thermodynamic Properties of Formic Acid.

Some Thermodynamic Properties of Formic Acid.

Photoionization, Structures, and Energetics of Na‐Doped Formic Acid–Water Clusters

Solubility of CO2 in Aqueous Formic Acid Solutions and the Effect of NaCl Addition: A Molecular Simulation Study

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Product

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Solubility of CO₂ in Aqueous Formic Acid Solutions and the Effect of NaCl Addition: A Molecular Simulation Study