Molecular Reorientation of Methanol in Mixtures with Carbon Tetrachloride

Gill, Dip Singh; Zeidler, Manfred

doi:10.1515/zna-1992-7-810

Zeitschrift Für Naturforschung A

1992

DOI: 10.1515/zna-1992-7-810

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Molecular Reorientation of Methanol in Mixtures with Carbon Tetrachloride

Dip Singh Gill

Manfred Zeidler

Abstract: Proton and oxygen-17 nmr relaxation rates of CD 3 17 OH as well as deuteron nmr relaxation rates of CH 3 OD were measured in mixtures with carbon tetrachloride at different compositions and temperatures. By varying the 17 0-content different contributions to the proton relaxation rate could be separated and from the 17 0-H dipolar interaction contribution the correlation time of the OH bond was determined. Using these correlation times the composition dependence of the deuterium and oxygen-17 quadrupole coupli… Show more

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Cited by 13 publications

References 28 publications

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Correlation Times and Quadrupole Coupling Constants in Liquid N‐Methylformamide and N‐Methylacetamide

Seipelt

Zeidler

1997

Ber Bunsenges Phys Chem

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Longitudinal 1H, 13C and 15N nmr relaxation rates were measured in the liquid phase for N‐methylformamide (NMF) over the temperature range 228–328 K and for N‐methylacetamide (NMA) over the range 300–378 K. Rotational correlation times were determined for the formyl C‐H and the N‐H bonds. The motion of both molecules is anisotopic, particularly that of N‐methylacetamide. The activation energies are 5.6 kJ/mol for C‐H and 19.7 kJ/mol for N‐H in NMF and 20.4–22.5 kJ/mol for N‐H in NMA. Quadrupole coupling constants were determined by relaxation measurements for the nuclei 14N and 2H. The quadrupole coupling constant for the amide deuteron in NMF is temperature dependent and varies from 193 to 206 kHz. For NMA this quadrupole coupling constant falls into the range 178 to 238 kHz. The quadrupole coupling constant for the formyl 2H in NMF (151–169 kHz) is temperature independet while for the 14N (NMF: 1.85–2.40 MHz; NMA: 1.65–2.45 MHz) it is temperature dependent.

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Correlation Times and Quadrupole Coupling Constants in Liquid N‐Methylformamide and N‐Methylacetamide

Seipelt

Zeidler

1997

Ber Bunsenges Phys Chem

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Orientational dynamics of hydrogen‐bonded liquids – A comparative study of dielectric and nuclear magnetic relaxation in n‐butanol‐tetrachloromethane mixtures

Nadolny

Volmari

Weingärtner

1998

Ber Bunsenges Phys Chem

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Complex dielectric spectra up to 20 GHz are measured at 25 "C 'for n-butanol tetrachloromethane mixtures.Within this frequency range the spectra can be described by two Debye-processes. Their relaxation times TI') and r12) are compared with the hypothetical single-particle relaxation time of the dipoles Z; estimated from deuteron magnetic relaxation rates in these mixtures. The results indicate a collective nature of the primary relaxation time rj", due to cooperative motion of several molecules. Although not accurate. in detail, some theoretical models can reproduce major features of the concentration dependence of TI'). In these models, r!') is coupled to r; via the Kirkwood correlation factor gl, which can be determined independently from the static permittivity. There is no obvious interrelation between 4 and the secondary relaxation time I\*', the nature of which remains puzzling.

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Dynamics of Methanol in Ionic Liquids: Validity of the Stokes–Einstein and Stokes–Einstein–Debye Relations

et al. 2014

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The validity of Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations for methanol in the physical environment of the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide is studied by means of nuclear magnetic resonance (NMR) relaxation time experiments, viscosity measurements and molecular dynamics (MD) simulations. The reorientational correlation times of the hydroxyl groups of pure methanol and of methanol in the IL/methanol mixtures were determined. For that purpose an approach for estimating NMR deuteron quadrupole coupling constants, presented by Wendt and Farrar (Mol. Phys. 1998, 95, 1077-1081), was confirmed. The self-diffusion coefficients of methanol were taken from the MD simulations. The viscosities of all systems were then measured and the SE and SED relations validated. For pure methanol both relations are valid, whereas they become increasingly invalid with increasing IL concentration, as indicated by effective volumes and radii that are too low. The deviation from the SE and SED relations could be related to dynamical heterogeneities described by the non-Gaussian parameter α(t) obtained from MD simulations. For pure methanol, α(t) is close to zero in accord with the validity of both relations. With increasing IL concentration the dynamical heterogeneities of methanol increase strongly. The times t* at the maximum of α(t) increase linearly with the relative number of methanol monomers in the mixtures. Thus, the dynamical heterogeneities are largest for single methanol molecules fully embedded in the IL environment. In their own environment methanol molecules are highly mobile, whereas in the IL-rich region the mobility is strongly reduced leading to the non-validity of SE and SED relations.

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Molecular Reorientation of Methanol in Mixtures with Carbon Tetrachloride

Cited by 13 publications

References 28 publications

Correlation Times and Quadrupole Coupling Constants in Liquid N‐Methylformamide and N‐Methylacetamide

Correlation Times and Quadrupole Coupling Constants in Liquid N‐Methylformamide and N‐Methylacetamide

Orientational dynamics of hydrogen‐bonded liquids – A comparative study of dielectric and nuclear magnetic relaxation in n‐butanol‐tetrachloromethane mixtures

Dynamics of Methanol in Ionic Liquids: Validity of the Stokes–Einstein and Stokes–Einstein–Debye Relations

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