The dipole moments and association of tri-n-octylammonium salts in solution

Sinitsyn, N.M.; Буслаева, Т. М.; Kartsev, G. N.; Ignat'eva, S. I.; Egorova, N. V.

doi:10.1007/bf00518760

Cited by 4 publications

(5 citation statements)

References 8 publications

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“…Thus, the WF increases with the OABr concentration to 4.8 eV. The alkylammonium salts exhibit dipole moments in the range of 5-11 Debye [83][84][85] and thus can easily induce a WF increase of +0.6 eV.…”

Section: Discussionmentioning

confidence: 99%

An efficient approach for controlling the crystallization, strain, and defects of the perovskite film in hybrid perovskite solar cells through antisolvent engineering

Tzoganakis

Chatzimanolis

Spiliarotis

et al. 2023

Sustainable Energy Fuels

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Section: Discussionmentioning

confidence: 99%

An efficient approach for controlling the crystallization, strain, and defects of the perovskite film in hybrid perovskite solar cells through antisolvent engineering

Tzoganakis

Chatzimanolis

Spiliarotis

et al. 2023

Sustainable Energy Fuels

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“…[40][41][42][43] Based on conductivity measurements, dipole-dipole interactions and hydrogen bonding have been hypothesized to cause aggregation of the ion-pairs. 44 Cryoscopic and ebullioscopic measurements in these solutions show that the aggregation of the organic species passes through a maxima as the amine concentration is increased, but the data interpretation is limited by the model assumptions. 45 Acid and water extraction trends have been studied with chemical equilibrium models under the assumption of constant aggregation of the organic phase species.…”

Section: Introductionmentioning

confidence: 96%

Speciation and organic phase structure in nitric acid extraction with trioctylamine

Nayak,

Servis,

Combs

et al. 2023

Preprint

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We report on the extraction of nitric acid from its aqueous solutions into organic solutions of trioctylamine (TOA) in toluene, investigated with spectroscopic, X-ray scattering, and computational tools to understand the molecular speciation in the organic phase and its relation to the nanoscale structure of the organic phase. Trends in acid and water extraction clearly show two and three regimes, respectively, but the speciation of nitric acid, water, and the amine in these regimes is not apparent. 1H-NMR of the organic phase shows that there are at least two distinct acidic protons in the organic phase while ATR-FTIR results show that the organic phase with excess acid extraction is a mixture of trioctylammonium-nitrate ion-pairs (TOAH.NO3) , and undissociated nitric acid molecules. IR spectra computed from DFT calculations performed with clusters of undissociated nitric acid molecule hydrogen-bonded with the anion of the trioctylammonium nitrate ion-pair are consistent with the ATR-FTIR results. We also show that the chain-like configurations of TOAH.NO3.HNO3.H2O are favored over TOAH.NO3$.H2O.HNO3, i.e., direct interaction between the two extracted nitric acid molecules is more favored compared to a water-mediated interaction. SAXS results of the organic phases were modeled as sums of Ornstein-Zernike scattering and a pre-peak feature at higher Q region, corresponding to features from density fluctuations and extractant packing, respectively. The extraction of undissociated nitric acid by the ion-pairs leads to an increased X-ray scattering contrast in the organic phase without any significant change in the Ornstein-Zernike correlation length. These results show that the organic phase nanostructure is more sensitive to the concentration of TOAH.NO3 and is relatively unaffected by excess acid extraction. These findings will enable a molecular understanding of the mechanisms behind metal extractions from acidic media with basic extractants.

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“…[32][33][34][35] Based on conductivity measurements, dipole-dipole interactions and hydrogen bonding have been hypothesized to cause aggregation of the ion pairs. 36 Cryoscopic and ebullioscopic measurements in these solutions show that aggregation of the organic species passes through a maxima as the amine concentration is increased, but the data interpretation is limited by the model assumptions. 37 Acid and water extraction trends have been studied with chemical equilibrium models under the assumption of constant aggregation of the organic phase species.…”

Section: Introductionmentioning

confidence: 96%

Speciation and organic phase structure in nitric acid extraction with trioctylamine

Nayak,

Servis,

Combs

et al. 2023

Preprint

View full text Add to dashboard Cite

Understanding chemical speciation and intermolecular interactions in multicomponent liquids is essential to understanding their phase behavior, which underpins chemical separation processes including solvent extraction. Here we report on the extraction of nitric acid from its aqueous solutions into organic solutions of trioctylamine (TOA) in toluene, investigated with spectroscopic, X-ray scattering, and computational tools to understand the molecular speciation in the organic phase and its relationship with the nanoscale structure of the organic phase. Trends in acid and water extraction clearly show two and three regimes, respectively, but the speciation of HNO3, water, and amine in these regimes is not apparent. 1H-NMR of the organic phase shows that there are at least two distinct acidic protons in the organic phase while ATR-FTIR results show that the organic phase with excess acid extraction is a mixture of trioctylammonium-nitrate ion pairs (TOAH.NO3), and undissociated HNO3 molecules. Comparison with DFT-computed IR spectra show that the chain-like configurations of TOAH.NO3.HNO3.H2O are favored over TOAH.NO3.H2O.HNO3, i.e., direct interaction between the two HNO3 molecules is more favored compared to a water-mediated interaction. SAXS of the organic phases were modeled as sums of Ornstein-Zernike (O-Z) scattering and a prepeak feature in the higher Q region, corresponding to features from density fluctuations and extractant packing, respectively. The extraction of undissociated HNO3 by the ion pairs leads to an increased X-ray scattering contrast in the organic phase without any significant change in the O-Z correlation length. These results show that the organic phase nanostructure is more sensitive to the concentration of TOAH.NO3 and is relatively unaffected by excess acid extraction. These findings will enable a molecular understanding of the mechanisms behind metal extractions from acidic media with basic extractants.

show abstract

The dipole moments and association of tri-n-octylammonium salts in solution

Cited by 4 publications

References 8 publications

An efficient approach for controlling the crystallization, strain, and defects of the perovskite film in hybrid perovskite solar cells through antisolvent engineering

An efficient approach for controlling the crystallization, strain, and defects of the perovskite film in hybrid perovskite solar cells through antisolvent engineering

Speciation and organic phase structure in nitric acid extraction with trioctylamine

Speciation and organic phase structure in nitric acid extraction with trioctylamine

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