Thermodynamic properties of the ethylammonium nitrate + water system: Partial molar volumes, heat capacities, and expansivities

Allen, Martin; Evans, D. F.; Lumry, Rufus

doi:10.1007/bf00649520

Cited by 63 publications

(30 citation statements)

References 13 publications

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“…It is interesting to see whether the alkyl ammonium nitrates also display some of these unique properties. This comparison has been already done for EAN by Evans et al [7][8][9]17] They could show that EAN possesses a number of similarities to water. In particular, the phase transfer of rare gases and hydrocarbons from cyclohexane to this PIL is accompanied by negative enthalpy and entropy changes.…”

mentioning

confidence: 86%

Hydrogen Bonding in Protic Ionic Liquids: Reminiscent of Water

2009

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Similarities and differences: Far-infrared spectra of protic ionic liquids could be assigned to intermolecular bending and stretching modes of hydrogen bonds. The characteristics of the low-frequency spectra resemble those of water. Both liquids form three-dimensional network structures, but only water is capable of building tetrahedral configurations. EAN: ethylammonium nitrate, PAN: propylammonium nitrate, DMAN: dimethylammonium nitrate.

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confidence: 86%

Hydrogen Bonding in Protic Ionic Liquids: Reminiscent of Water

2009

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“…Data on entropy and heat capacities for alkylammonium nitrates, with the exception of ammonium nitrate, do not appear to be available. Perry et al (1997), h Cottrell and Gill (1951), i Allen et al (1985), j Yaws (2003), k Wagman et al (1982) One approach is to extract the entropy information from atomistic classical and quantum simulation. Lin et al (2003) developed a 2-phase thermodynamic approach for calculating the thermodynamic properties of complex systems from single molecular dynamics simulation trajectories.…”

Section: Appendix Amentioning

confidence: 99%

Secondary aerosol formation from atmospheric reactions of aliphatic amines

et al. 2007

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Abstract. Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NO x with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R 3 NH + ) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant nonsalt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

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“…Up to now, most publications dealing with the dynamics of ILs and their mixtures with non-ionic compounds have focused on salts with 1-alkyl-3-methylimidazolium cations [9][10][11][12][13] but only little is known about PIL-containing systems. 14,15 In this contribution we present a first systematic study of the cooperative dynamics of EAN + dipolar aprotic solvent mixtures. Acetonitrile (AN) was chosen as the non-ionic component as this industrially important solvent 16,17 is miscible with EAN over the entire composition range.…”

Section: Introductionmentioning

confidence: 99%

Do H-bonds explain strong ion aggregation in ethylammonium nitrate + acetonitrile mixtures?

Sonnleitner

Nikitina

Nazet

et al. 2013

Phys. Chem. Chem. Phys.

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Binary mixtures of the protic ionic liquid ethylammonium nitrate (EAN) and acetonitrile (AN) were studied at 25 1C over the entire composition range by means of broadband dielectric spectroscopy covering 0.2 r n/GHz r 89. The dielectric spectra could be decomposed into two relaxation processes, both of which proved to be composite modes. For dilute solutions the higher-frequency Debye relaxation centered at B60 GHz is associated with the rotational diffusion of AN molecules, whereas at higher salt concentrations ultra-fast intermolecular vibrations and librations of EAN dominate the process. For EAN-rich solutions the lower-frequency relaxation is mainly due to jump reorientation of the ethylammonium cation, whereas contact ion pairs (CIPs) dominate this mode for dilute solutions. From the relaxation amplitudes effective solvation numbers and ion-pair concentrations were determined. For vanishing EAN mole fraction, x EAN -0, an effective cation solvation number of B7 was found which steeply drops until x EAN E 0.2 but shows only moderate decrease later on. The obtained association constant for EAN, K 0 A = 970 L mol À1 , exceeds that of other 1 : 1 electrolytes in AN by a factor of B30-50. This observation, as well as the fact that CIPs are formed despite strong cation solvation, indicates that ion pairing is mainly driven by the formation of strong hydrogen bonds between anions and cations.

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Thermodynamic properties of the ethylammonium nitrate + water system: Partial molar volumes, heat capacities, and expansivities

Cited by 63 publications

References 13 publications

Hydrogen Bonding in Protic Ionic Liquids: Reminiscent of Water

Hydrogen Bonding in Protic Ionic Liquids: Reminiscent of Water

Secondary aerosol formation from atmospheric reactions of aliphatic amines

Do H-bonds explain strong ion aggregation in ethylammonium nitrate + acetonitrile mixtures?

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