High Pressure NMR Studies of Confined Liquids

1992 ◽  
Vol 290 ◽  
Author(s):  
J. Jonas ◽  
Jing Zhang ◽  
Shu Xu
Keyword(s):  
Surface Layer ◽  
Rotational Diffusion ◽  
Relaxation Times ◽  
Porous Silica ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Nmr Studies ◽  
Silica Glasses ◽  
Spin Lattice ◽  
Confined Liquids

AbstractThe main goal of our novel NMR experiments on confined liquids was to determine the effects of pressure on the dynamics of liquids in the surface layer by using the twostate, fast exchange model and compare them to the pressure effects observed for bulk liquids. With this goal in mind, the deuteron NMR spin-lattice relaxation times, T1, in liquid pyridine-d5, nitrobenzene-d5, and methylcyclohexape-d confined to sol-gel porous silica glasses with pore radii in the range from 18Å to 49˚A were measured as a function of pressure up to 5 kbar at 300 K. In another set of high resolution natural abundance 13C NMR experiments, the 13C relaxation behavior of each carbon in 2- ethylhexyl benzoate model lubricant was measured as a function of pressure in porous silica glasses. In fact, the described experimental approach which allows investigation of the effects of pressure on the dynamic behavior of surface-layer liquids, may provide a new tool in studies of model liquid lubricants at extreme conditions of pressure and temperature. In addition selected results of a recent study of acetonitrile-d3 are reviewed. The 2H and 14N spin-lattice relaxation times of acetonitrile-d3 in porous silica glasses were measured in order to study the confinement effects on the anisotropic reorientation characterized by rotational diffusion constants, D⊥ and D‖, of this symmetric-top molecule.

Dynamics of Liquids in Confined Geometries

1994 ◽  
Vol 346 ◽  
Author(s):  
Shu Xu ◽  
J.-P. Korb ◽  
J. Jonas
Keyword(s):  
Surface Layer ◽  
Porous Silica ◽  
Lattice Relaxation ◽  
Pressure Effects ◽  
Spin Lattice Relaxation ◽  
Simple Liquid ◽  
Relaxation Rates ◽  
Confined Geometries ◽  
Nmr Studies ◽  
Silica Glasses

ABSTRACTAn overview of several NMR studies of liquids in confined geometries is presented. First, the NMR relaxation rates, 1/T1, 1/T1ρ , and 1/T2 were measured for several molecular liquids confined to porous silica glasses with pore radii in the range from 12 Å to 100 Å as a function of temperature, pore size, and frequency. The experimental relaxation data were interpreted in terms of bulk, surface, and topological contributions using the following expression:where 1/Tib and 1/Tis are the bulk and the surface layer relaxation rates, ε is the thickness of the surface layer, R is the pore radius, and Ai(ω) represents the pure topological effect.Second, the pressure effects on the dynamics of the confined liquid of acetonitrile-d3 were also investigated. Third, the natural abundance of 13C spin lattice relaxation rates for CS2 confined to porous silica glasses provided information about confinement effects on the angular momentum behavior of this simple liquid.

scholarly journals 15N and 133Cs Solid NMR Studies on Ionic Dynamics in Plastic CsNO2

1996 ◽  
Vol 51 (5-6) ◽  
pp. 761-768 ◽  
Author(s):  
H. Honda ◽  
M. Kenmotsu ◽  
N. Onoda-Yamamuro ◽  
H. Ohki ◽  
S. Ishimaru ◽  
...  
Keyword(s):  
Phase Ii ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Temperature Phase ◽  
Nmr Studies ◽  
Self Diffusion ◽  
Spin Lattice ◽  
Solid Nmr ◽  
Plastic Phase

The temperature dependence of the 15N and 133Cs NMR spin-lattice relaxation times, the 15N spin-spin relaxation time, and the 15N and 133Cs spectra of CsNO2 was observed in the plastic phase (209.2 < T < 673 K (m. p.)) and the low-temperature phase (Phase II). In Phase II we found the NO-2 180°-flip, which could be attributed to the anomalous increase of the heat capacity curve, and determined the activation energy of this motion to be 8.7-11.7 kJ mol-1. The 15N and 133Cs spectra in this phase are inconsistent with the reported crystal structure R3̅m and can be explained by lower crystal symmetry. In the plastic phase we detected a new anionic motion with 11 kJ mol-1 , an isotropic NO-2 reorientation with 8.5-9 kJ mol-1, and ionic self-diffusion with 47 kJ mol-1. The presence of ionic self-diffusion was confirmed by measuring the electrical conductivity.

Nuclear Magnetic Resonance Studies of Molecular Motion in Natural Rubber

1963 ◽  
Vol 36 (2) ◽  
pp. 318-324
Author(s):  
W. P. Slichter ◽  
D. D. Davis
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Natural Rubber ◽  
Molecular Motion ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Nmr Studies ◽  
Spin Lattice ◽  
Nuclear Magnetic

Abstract Nuclear magnetic resonance measurements have been made on natural rubber to examine how frequency, temperature, and crystallinity affect the nuclear relaxation. Moecular motions were studied by observing NMR linewidths and spin-lattice relaxation times at temperatures between −100° and 100° C, and at radio frequencies between 2 and 60 Mc. The effect of crystallinity was seen in measurements on stark rubber. The relation between frequency and temperature in the spin-lattice relaxation process is examined in terms of the Arrhenius equation and the WLF expression. The importance of using frequency as a variable in NMR studies of molecular motion is stressed.

scholarly journals NMR Studies on Dynamics of Water Intercalated in Clay Minerals

1999 ◽  
Vol 54 (6-7) ◽  
pp. 431-436 ◽  
Author(s):  
Shin’ichi Ishimaru ◽  
Ryuichi Ikeda
Keyword(s):  
Nmr Spectra ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Axial Rotation ◽  
Spin Lattice Relaxation ◽  
Water Molecules ◽  
Nmr Studies ◽  
Spin Lattice ◽  
H Nmr ◽  
Clay Layers

Abstract The dynamics of water molecules intercalated in D2O saturated synthetic and natural smectites, and a synthetic Na-fluormica were studied by measurements of solid state 2H NMR spectra and spin-lattice relaxation times at 150 - 370 K. The obtained results could be explained by the 2-site flip, the C2 rotation and the isotropic rotation of the D2O molecules in smectites. In fluormica, the isotropic motion was undetectable, but the axial rotation of the hydration sphere as a whole was observed. The activation energies and correlation times of the C2 rotation were almost independent of the interlayer cations but depended on the character of clay-layers.

Solid-state 2H NMR study of methyl-d3-cobalamin

1998 ◽  
Vol 76 (2-3) ◽  
pp. 423-428 ◽  
Author(s):  
Jennifer R Garbutt ◽  
Gillian R Goward ◽  
Christopher W Kirby ◽  
William P Power
Keyword(s):  
Solid State ◽  
Rotational Diffusion ◽  
Group Analysis ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Methyl Group ◽  
Spin Lattice ◽  
H Nmr ◽  
Nmr Study

A solid-state 2H NMR study of methyl-d3-cobalamin has been performed as a function of temperature to provide information concerning the character and energetics of the motion performed by this unique bioorganometallic methyl group. Analysis of the 2H NMR line shape indicates that the methyl group undergoes rapid three-fold rotation, and that the Co-C-2H angle lies between 105.9 and 109.5°. Determination of the spin-lattice relaxation times T1 shows that the relaxation is anisotropic, consistent with a "jumping" motion of the methyl group rather than rotational diffusion. This also provides the activation energy to methyl jumps as 8.3 ± 1.3 kJ/mol. It is proposed that this energetic barrier may be a useful probe of changes in the electronic character of the Co-C bond that accompany the biological role of this molecule in such enzymes as methionine synthase.Key words: cobalamin, solid-state NMR, deuterium NMR, molecular dynamics.

Pulsed NMR studies in solid H2. III. Spin-lattice relaxation times

1983 ◽  
Vol 53 (5-6) ◽  
pp. 585-617 ◽  
Author(s):  
S. Washburn ◽  
M. Calkins ◽  
H. Meyer ◽  
A. B. Harris
Keyword(s):  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Nmr Studies ◽  
Spin Lattice ◽  
Pulsed Nmr

scholarly journals Order–disorder transitions in adamantane derivatives: vibrational spectroscopic and 13C NMR studies of 1-chloroadamantane

1993 ◽  
Vol 71 (11) ◽  
pp. 1890-1897 ◽  
Author(s):  
Yining Huang ◽  
Ralph M. Paroli ◽  
D.F.R. Gilson ◽  
I.S. Butler
Keyword(s):  
Variable Temperature ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Adamantane Derivatives ◽  
Scanning Calorimetry ◽  
Nmr Studies ◽  
Spin Lattice ◽  
Two Phases ◽  
C Nmr

The order–disorder behaviour of 1-chloroadamantane (1-C10H15Cl) has been investigated by differential scanning calorimetry, and variable-temperature vibrational and 13C NMR spectroscopy. The factor group splittings in the vibrational spectra are in accord with the known crystal structures of the two phases. The 13C spin-lattice relaxation times and dipolar dephasing measurements have been analysed to give the barriers to rotation in both phases and to determine the nature of the rotations in each phase. In the ordered phase, the motion is limited to rotation about the molecular axis. In the disordered phase, additional motions occur about axes through the tertiary carbon atoms.

NQR and NMR Studies of Phase Transitions in R2Pb[Cu(NO2)6] (R = K, Rb, Tl, Cs, and NH4)

1996 ◽  
Vol 51 (5-6) ◽  
pp. 721-725
Author(s):  
Motohiro Mizuno ◽  
Tetsuo Asaji ◽  
Masahiko Suhara ◽  
Yoshihiro Furukawa
Keyword(s):  
Transition Point ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Incommensurate Phase ◽  
The Other ◽  
Spin Lattice Relaxation ◽  
Nmr Studies ◽  
Spin Lattice ◽  
H Nmr ◽  
The Difference

Abstract39K, 87, 85Rb, 133Cs, 205T1, and 1, 2H NMR spin-lattice relaxation times T1 and 14N NQR spin-lattice relaxation times T1Q were determined for R2Pb[Cu(NO2)6] (R = K, Rb, Tl, Cs, and NH4). T1 of 39K and 87Rb showed very short values in the incommensurate phase as compared with those in the other phases. When the commensurate-incommensurate phase transition point is approached from below, 14N T1Q of the R = K, Rb, Tl, and NH4 compounds showed rapid decrease. On the other hand, that of the R = Cs compound began to decrease first after passing beyond the corresponding transition point. The difference of the T1Q behavior may be ascribed to the difference of the condensed phonon mode in the incommensurate phase.

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