Quantum-chemical simulation of dicyanamide and tricyanomethanide ion solvation

Garbuz, S. V.; Skopenko, V. V.; Khavryuchenko, V. D.; Gerasimchuk, Nikolay

doi:10.1007/bf00580304

Cited by 2 publications

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“…First synthesized in 1925, the dicyanamide anion N(CN) 2 - and particularly its transition metal salts have recently attracted considerable attention, − because of their potential use as molecular magnets and multifunctional materials. The structures and properties of many dicyanamide salts have been characterized by a variety of spectroscopic techniques. − ,, Bare N(CN) 2 - anion is a prototype of a class of five-atom, 24-valence electron chainlike molecules, , and its high stability has inspired theoretical searches for other isoelectronic species, such as N 5 + and OCNCO + . − Organic salts of N(CN) 2 - have recently been discovered to be low-viscosity room-temperature ionic liquids . Vibrational spectroscopy and dynamics of N(CN) 2 - in solution have been carried out to elucidate the interactions of N(CN) 2 - with different solvents, as well as simulations by molecular force field…”

Section: Introductionmentioning

confidence: 99%

Microsolvation of the Dicyanamide Anion: [N(CN)₂^-](H₂O)_n (n = 0−12)

et al. 2007

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Photoelectron spectroscopy is combined with ab initio calculations to study the microsolvation of the dicyanamide anion, N(CN)(2)(-). Photoelectron spectra of [N(CN)(2)(-)](H2O)n (n = 0-12) have been measured at room temperature and also at low temperature for n = 0-4. Vibrationally resolved photoelectron spectra are obtained for N(CN)(2)(-), allowing the electron affinity of the N(CN)2 radical to be determined accurately as 4.135 +/- 0.010 eV. The electron binding energies and the spectral width of the hydrated clusters are observed to increase with the number of water molecules. The first five waters are observed to provide significant stabilization to the solute, whereas the stabilization becomes weaker for n > 5. The spectral width, which carries information about the solvent reorganization upon electron detachment in [N(CN)(2)(-)](H2O)n, levels off for n > 6. Theoretical calculations reveal several close-lying isomers for n = 1 and 2 due to the fact that the N(CN)(2)(-) anion possesses three almost equivalent hydration sites. In all the hydrated clusters, the most stable structures consist of a water cluster solvating one end of the N(CN)(2)(-) anion.

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Section: Introductionmentioning

confidence: 99%

Microsolvation of the Dicyanamide Anion: [N(CN)₂^-](H₂O)_n (n = 0−12)

et al. 2007

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“…This is due to the strong hydrogen bonding between the dicyanamide anion and 1-butanol. The hydrogen bond energy between dicyanamide ion with butanol (60.8 kJ/mol) is greater as compared to that with water (53.9 kJ/mol). This is contrary to the measurements by Freire et al where [TDTHP][DCA] and [TDTHP][DEC] were found to be more miscible with water.…”

Section: Resultsmentioning

confidence: 90%

“…It can be seen from Figures and that the amount of water content in [TDTHP][DEC] is greater as compared to that of [TDTHP][DCA]. This is attributed to a larger electronegativity atom in [DEC] thereby forming a strong bond with water …”

Section: Resultsmentioning

confidence: 98%

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Experimental and Theoretical Studies on the Effectiveness of Phosphonium-Based Ionic Liquids for Butanol Removal at T = 298.15 K and p = 1 atm

Rabari

Banerjee

2014

Ind. Eng. Chem. Res.

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Biobutanol obtained via an acetone–butanol–ethanol (ABE) fermentation process is now considered a potential biofuel. In recent times low density phosphonium cations were found to remove butanol from aqueous solutions. In this regard, low density phosphonium-based ionic liquids (ILs) trihexyl(tetradecyl)phosphonium dicyanamide [TDTHP][DCA] and trihexyl(tetradecyl)phosphonium decanoate [TDTHP][DEC] have been used for the separation of 1-butanol from aqueous solution. Ternary liquid–liquid equilibrium data for IL(1)–1-butanol(2)–water(3) are measured at T = 298.15 K and p = 1 atm. Butanol partition coefficients are obtained in the range of 25–85 and 20–290 for [TDTHP][DCA] and [TDTHP][DEC], respectively. 1H NMR spectra indicates the absence of IL and water in the raffinate and extract phase, respectively. This experimentally confirms that there will be negligible cross-contamination of water and IL in either phase. The separation factor of butanol over water approaches infinity for both systems. A wider spread of binodal curve indicated a higher recovery of butanol at different feed concentrations. The experimental data were compared with excess Gibb’s free energy models, namely the nonrandom two liquid (NRTL) and the universal quasichemical (UNIQUAC) models. NRTL and UNIQUAC gave root mean square deviation (RMSD) values in the range of 0.12–0.14% and 0.48–0.55%, respectively, for both ILs. Further the predictive ability of a statistical mechanical framework was also performed using the well-known COSMO-RS model. The COSMO-RS model gave RMSD values of 18.67% and 16.21% for the systems containing the ILs respectively, [TDTHP][DCA] and [TDTHP][DEC].

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Quantum-chemical simulation of dicyanamide and tricyanomethanide ion solvation

Cited by 2 publications

References 3 publications

Microsolvation of the Dicyanamide Anion: [N(CN)₂^-](H₂O)_n (n = 0−12)

Microsolvation of the Dicyanamide Anion: [N(CN)₂^-](H₂O)_n (n = 0−12)

Experimental and Theoretical Studies on the Effectiveness of Phosphonium-Based Ionic Liquids for Butanol Removal at T = 298.15 K and p = 1 atm

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Quantum-chemical simulation of dicyanamide and tricyanomethanide ion solvation

Cited by 2 publications

References 3 publications

Microsolvation of the Dicyanamide Anion: [N(CN)2-](H2O)n (n = 0−12)

Microsolvation of the Dicyanamide Anion: [N(CN)2-](H2O)n (n = 0−12)

Experimental and Theoretical Studies on the Effectiveness of Phosphonium-Based Ionic Liquids for Butanol Removal at T = 298.15 K and p = 1 atm

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Microsolvation of the Dicyanamide Anion: [N(CN)₂^-](H₂O)_n (n = 0−12)

Microsolvation of the Dicyanamide Anion: [N(CN)₂^-](H₂O)_n (n = 0−12)