Glutaronitrile. Calorimetrically Determined Thermal Properties from 5 to 350°K. and Statistical Gaseous Entropy<sup>1a</sup>

Clever, H. Lawrence; Wulff, Claus A.; Westrum, Edgar F.

doi:10.1021/j100890a031

Cited by 12 publications

(13 citation statements)

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“…Both these facts are consistent with there being no large scale molecular reorientational motion in solid I and so confirms the conclusion in [25] that malononitrile has no plastic phase. Succinonitrile (CN(CH2)2CN) therefore differs markedly from its neighbours, glutaronitrile [26] (CN(CHz)3CN) and malononitrile (CNCH2CN) in having a plastic phase.…”

Section: Malononitrile Malononitrilementioning

confidence: 99%

Molecular motion in succinonitrile and malononitrile by nuclear magnetic resonance

1969

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Measurements are reported of the proton spin-lattice relaxation time, T1, at 21 "5 and 14"3 MHZ and the relaxation time in the rotating frame, Tip, at 14" 3 MHZ for HI = 7" 1 G, in liquid and solid polycrystalline succinonitrile, (CH2CN)2. Correlation times for molecular reorientation and diffusion have been obtained. In the liquid these agree with dielectric correlation times. In the upper temperature solid phase I, the N.M.R. reorientational correlational time has an Arrhenius behaviour with an activation energy greater than in the liquid and only agrees with the dielectric correlation time at lower temperatures. Reasons for the discrepancy at higher temperatures are discussed and an anomaly pointed out by Clemett and Davies [10] is resolved. At higher temperatures in phase I, Tip is controlled by translational diffusion modulated interactions, as also, possibly, is T1 just below the triple point. Values for the translational correlation time are obtained. It seems possible that a 'defect diffusion' mechanism [24] is active in this substance rather than the lattice diffusion usually accepted in plastic crystals with simpler globular molecules. It is confirmed that no large scale molecular motion occurs in the lower temperature phase II.It has been shown that malononitrile, CH2(CN)~, does not have a plasticcrystal phase.

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Section: Malononitrile Malononitrilementioning

confidence: 99%

Molecular motion in succinonitrile and malononitrile by nuclear magnetic resonance

1969

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“…This expected positive contribution to the disorder during the addition of IL is explained by fewer GLN–GLN interactions in favor of more cation–GLN and anion–GLN interactions. Note, that S 0 and U POT , estimated for GLN with the same empirical relationships (eqs and ), are adjusted for ILs and probably less suited to molecular solvents such as GLN, which explains the difference observed with the literature for S 0 …”

Section: Resultsmentioning

confidence: 99%

“…Note, that S 0 and U POT , estimated for GLN with the same empirical relationships (eqs 6 and 7), are adjusted for ILs and probably less suited to molecular solvents such as GLN, which explains the difference observed with the literature for S 0 . 66 3.1.2. Viscosity.…”

Section: Resultsmentioning

confidence: 99%

Comparative Study of Physical Properties and CO₂ Solubility of Ammonium and Sulfonium Ionic Liquids in Mixture with Glutaronitrile

2020

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In this work, we present a comparative study of physical properties and CO2 solubility of two ionic liquids (ILs), protic trimethylammonium bis[(trifluoromethyl)sulfonyl]imide and aprotic trimethylsulfonium bis[(trifluoromethyl) sulfonyl]imide in mixture with glutaronitrile (GLN). The effect of temperature on density and viscosity of mixtures was studied and discussed in terms of intra- and intermolecular interactions. Applying Glasser’s theory, standard molar entropy, S 0, and the crystal energy, U POT, of the IL/GLN mixtures were estimated, showing a positive contribution of ILs to these quantities. This positive contribution to the entropy variation by the addition of an IL is because of the fact that it destroys GLN–GLN interactions, replacing them with new cation–GLN and anion–GLN interactions. The deconstructing effect of S111 is greater because there are no strong S111–GLN interactions, unlike the ammonium cation which can establish H-bonds with CN groups. The CO2 solubilities in both (IL/GLN) mixtures expressed by CO2 molar fractions, x CO2 , or the Henry constant K H/MPa showed that the [S111][TFSI]/GLN solubilizes more CO2 than the [HN111][TFSI]/GLN throughout the temperature range. The solubility of CO2 is sensitive to the cation nature and temperature. The sulfonium cation promotes CO2 solubility because it is less cluttered than the ammonium cation unlike HN111, which is the hydrogen-binding seat (NH–GLN) with GLN. Finally, the thermodynamic parameters such as the standard enthalpy Δdiss H 0, the free enthalpy Δdiss G 0, and the entropy Δdiss S 0 of CO2 dissolution were calculated. They showed that the dissolution of CO2 did not depend on the molecular organization (small variation in entropy) but that it is linked to the intermolecular interactions in the IL/GLN mixture, as shown by the difference in Δmix H.

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“…those for maloninitrile [1,32,34] and succinonitrile [2]. The investigations of glutaronitrile only provided evidence of the existence of a metastable phase crystal II but the thermodynamic parameters of its transition to crystal I were not determined [4].…”

Section: Solid-to-solid Transitionsmentioning

confidence: 99%

“…Alkane-a,xdinitriles (hereinafter called alkyldinitriles) are an industrially important class of compounds whose thermodynamic properties have received little attention. The thermodynamics of their solid-to-solid and solid-to-liquid phase transitions have only been investigated for the first three members of the series, malononitrile [1], succinonitrile [2,3] and glutaronitrile [4]. This paper provides an overall picture of the solid phase behaviour of 11 linear alkyldinitriles NC-(CH 2 ) n -CN, where n = (1 to 10 and 12).…”

Section: Introductionmentioning

confidence: 99%

Fusion and solid-to-solid transitions of a homologous series of alkane-α,ω-dinitriles

Badea

Blanco

Gatta

2007

The Journal of Chemical Thermodynamics

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Glutaronitrile. Calorimetrically Determined Thermal Properties from 5 to 350°K. and Statistical Gaseous Entropy^1a

Cited by 12 publications

References 0 publications

Molecular motion in succinonitrile and malononitrile by nuclear magnetic resonance

Molecular motion in succinonitrile and malononitrile by nuclear magnetic resonance

Comparative Study of Physical Properties and CO₂ Solubility of Ammonium and Sulfonium Ionic Liquids in Mixture with Glutaronitrile

Fusion and solid-to-solid transitions of a homologous series of alkane-α,ω-dinitriles

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Glutaronitrile. Calorimetrically Determined Thermal Properties from 5 to 350°K. and Statistical Gaseous Entropy1a

Cited by 12 publications

References 0 publications

Molecular motion in succinonitrile and malononitrile by nuclear magnetic resonance

Molecular motion in succinonitrile and malononitrile by nuclear magnetic resonance

Comparative Study of Physical Properties and CO2 Solubility of Ammonium and Sulfonium Ionic Liquids in Mixture with Glutaronitrile

Fusion and solid-to-solid transitions of a homologous series of alkane-α,ω-dinitriles

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Glutaronitrile. Calorimetrically Determined Thermal Properties from 5 to 350°K. and Statistical Gaseous Entropy^1a

Comparative Study of Physical Properties and CO₂ Solubility of Ammonium and Sulfonium Ionic Liquids in Mixture with Glutaronitrile