Vapor Pressures of Perdeuterobenzene and of Perdeuterocyclohex ane

Davis, R. T.; Schiessler, Robert W.

doi:10.1021/j150510a027

Cited by 26 publications

(13 citation statements)

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“…From the ρ values for PS, PI, and d 6 - benzene, the increase in intensity indicated the solvent partitioned preferentially into the PS domains of the film; the d 6 - benzene mixed with the PS increased the contrast ([Δρ] 2 ) relative to d 6 - benzene mixed with PI ([Δρ] 2 = [ρ PS/ d 6 ‑benzene – ρ PI /d 6 ‑benzene ] 2 ). Literature data are consistent with the solvent preference determined herein, as the d 6 - benzene solubility parameter (δ d 6 ‑benzene ≈ 18.8 MPa 1/2 ) and literature χ poly–sol values ([χ PS–benzene = 0.37] and [χ PI–benzene = 0.44]) indicate that d 6 - benzene is considered slightly preferential for PS over PI …”

Section: Results and Discussionsupporting

confidence: 89%

Tracking Solvent Distribution in Block Polymer Thin Films during Solvent Vapor Annealing with in Situ Neutron Scattering

et al. 2016

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Herein, we employed in situ small-angle neutron scattering (SANS) and neutron reflectivity (NR) to elucidate the importance of polymer–solvent interactions on morphology development during solvent vapor annealing (SVA) of block polymer (BP) thin films. Judicious choice of nanostructure orientation (parallel to the substrate) permitted measurement of the preferential segregation of solvent (d 6-benzene) into our cylinder-forming poly(styrene-b-isoprene-b-styrene) (SIS) films. A distinguishing feature of this work is the simultaneous tracking of nanostructure evolution and solvent segregation, enabled through the combination of SANS (in-plane features), NR (out-of-plane features), and solvent deuteration, which directly related polymer–solvent interactions to morphology reorganization. We found that at higher d 6-benzene partial pressures (p/p sat) the number of cylinder layers (domains) increased or decreased to accommodate overall film thickness changes upon swelling/deswelling, while the SIS domain spacing remained nearly constant. However, at lower p/p sat values, the SIS domain spacing changed to accommodate similar swelling/deswelling variations, while the number of layers remained invariant. The threshold for this p/p sat transition was directly related to plasticization of the polystyrene (PS) block, which has significant implications on the size of the domains, degree of ordering, and interfacial roughness. Thus, by linking polymer–solvent interactions to morphology evolution, we have developed an improved understanding of the interplay between the kinetic and thermodynamic effects that can direct the self-assembly and through-film periodicity of nanostructured thin films.

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Section: Results and Discussionsupporting

confidence: 89%

Tracking Solvent Distribution in Block Polymer Thin Films during Solvent Vapor Annealing with in Situ Neutron Scattering

et al. 2016

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“…The values obtained from exact vapour pressure measurements are 1.0745 [29] and 1.0302 [30] resp. For heptane we obtain a value of 1.113 for 91"…”

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confidence: 99%

The Gas‐Chromatographic Retention Indices of Deuterated Compounds

Gäumann

Bonzo

1973

Helvetica Chimica Acta

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Zusammenfassung. Die h d e r u n g des Retentionsindex mit dem Deuterierungsgrad ciniger Verbindungen wurden als Funktion der Temperatur und der stationaren Phase untersucht. Er zeigt grossc Regelmassigkeiten in der Abhangigkeit von der Anzahl der Deuteriumatome in der Molekel und von der stationaren Phase. Die Resultate gestatten eine Abschatzung der relativen Fluchtigkeit G( einer deuterierten Verbindung und der h d e r u n g der thermodynamischen Zustandsfunktionen bei der Deuterierung. With this in mind, we published a procedure that permits the determination of the isotopic distribution in a compound, even when the gas-chromatographic resolution does not allow the determination of the different isotope-isomeric species separately [24]. We have since used gas-chromatographic analysis as a routine procedure to measure deuterium distributions in different compounds. A literature survey shows that there is very little systematic data accumulated in this field. This in why we have collected some of our results of the past few years in order to facilitate research in this field. Because of the author's interest, most of the compounds studied are paraffins. We think that this should not invalidate some of the generalizations found, however.

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“…Although the vaporization enthalpies calculated by the correlation differ from the recommended values by a few tenths of a kilojoule, the reproducibility of the results in runs 1 and 2 and runs 3 and 4 is considerably better. If the vaporization enthalpies at T = 298.15 K for benzene and toluene are calculated using the vapor pressures reported in the vapor pressure isotope studies from T = 283.15 K to T = 313.15 K (from plots of ln p vs 1/ T ), mean vaporization enthalpies for labeled and unlabeled cyclohexane – and labeled and unlabeled benzene – of {(33.05 ± 0.4), (33.32 ± 0.065), (34.28 ± 0.24), and (34.24 ± 0.25)} kJ·mol −1 are calculated. The uncertainties represent two standard deviations of the mean.…”

Section: Methodsmentioning

confidence: 99%

“…With deuterated molecules, both normal ( p H / p D > 1) and inverse vapor pressure isotope effects ( p H / p D < 1) have been reported . Relatively few vapor pressure and vaporization enthalpy measurements have been reported for larger perdeuterated hydrocarbons, and with the exception of compounds with exchangeable hydrogens (such as alcohols, amines, and acids), cyclohexane- d 12 and benzene- d 6 are the only hydrocarbons for which vapor pressure data for the liquid state are readily available. – The vapor pressures of cyclohexane- d 12 and benzene- d 6 have been repeatedly measured, and the most recent results generally are in very good agreement. – For most hydrocarbons studied, inverse vapor pressure isotope effects have generally been observed, p D > p H …”

Section: Introductionmentioning

confidence: 99%

Enthalpies of Vaporization and Vapor Pressures of Some Deuterated Hydrocarbons. Liquid−Vapor Pressure Isotope Effects

et al. 2008

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Liquid-vapor pressures as a function of temperature and enthalpies of vaporization of a series of both liquid and solid hydrocarbons and their perdeuterated analogues have been determined by correlation-gas chromatography. The applicability of this technique is first demonstrated by reproducing the vapor pressure isotope effect of cyclohexane-d 12 and benzene-d 6 . Other hydrocarbons studied include the perdeuterated forms of hexane, toluene, heptane, the p-and o-xylenes, naphthalene, biphenyl, acenaphthene, phenanthrene, anthracene, hexamethylbenzene, p-terphenyl, perylene, and chrysene. Vapor pressures and vaporization enthalpies of unlabeled hexamethylbenzene and perylene are also reported. Inverse vapor pressure isotope effects of the liquid phase are observed for all the substances examined. Vaporization enthalpy differences between unlabeled and labeled hydrocarbons are small and generally slightly positive. Vapor pressure-temperature relationships are reported in the form of a third-order polynomial that appears to reproduce experimental liquid-vapor pressures from T ) 298.15 K to the boiling temperature.

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Vapor Pressures of Perdeuterobenzene and of Perdeuterocyclohex ane

Cited by 26 publications

References 0 publications

Tracking Solvent Distribution in Block Polymer Thin Films during Solvent Vapor Annealing with in Situ Neutron Scattering

Tracking Solvent Distribution in Block Polymer Thin Films during Solvent Vapor Annealing with in Situ Neutron Scattering

The Gas‐Chromatographic Retention Indices of Deuterated Compounds

Enthalpies of Vaporization and Vapor Pressures of Some Deuterated Hydrocarbons. Liquid−Vapor Pressure Isotope Effects

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