A nuclear magnetic resonance study of 1H, 23Na, and 31P relaxation and molecular dynamics in the sodium salts of some pyrophosphates

1989 ◽  
Vol 67 (6) ◽  
pp. 592-598 ◽  
Author(s):  
E. C. Reynhardt
Keyword(s):  
Relaxation Times ◽  
Lattice Relaxation ◽  
Laboratory Frame ◽  
Nuclear Magnetic Resonance Study ◽  
Spin Lattice Relaxation ◽  
Molecular Reorientation ◽  
Temperature Range ◽  
Spin Lattice ◽  
Second Moments ◽  
31P Relaxation

Proton second moments and spin-lattice relaxation times in the laboratory and rotating frames and 31P and 23Na spin-lattice relaxation times in the laboratory frame have been measured over the temperature region 295 > T > 100 K for the sodium pyrophosphate salts, Na2P2O7∙10H2O and Na2H2P2O7. Laboratory-frame 31P and 23Na spin-lattice relaxation times have also been measured over the same temperature range for Na4P2O7. In the case of Na4P2O7∙10H2O, the results show clearly that the H2O molecules execute a twofold jump motion at higher temperatures. The potential barriers to these motions range from 30 to 40 kJ/mol. The 31P and 23Na relaxations are also influenced by these motions. The [Formula: see text] ion in Na2H2P2O7 is stationary over the temperature range studied. T1(Na) is most probably dominated by acoustical lattice vibrations. The [Formula: see text] ion in Na4P2O7 is not involved in a molecular reorientation. A shallow T1(P) minimum of 55 s is associated with a limited motion of the pyrophosphate molecule.

The effects of high temperatures (29–123 °C) on critical micelle concentrations in solutions of potassium n-octanoate in deuterium oxide: A nuclear magnetic resonance study

1986 ◽  
Vol 64 (9) ◽  
pp. 1823-1828 ◽  
Author(s):  
M. A. Desando ◽  
L. W. Reeves
Keyword(s):  
Chemical Shifts ◽  
Deuterium Oxide ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Nuclear Magnetic Resonance Study ◽  
Spin Lattice Relaxation ◽  
Spectral Parameters ◽  
Critical Micelle Concentrations ◽  
Temperature Range ◽  
Spin Lattice

Critical micelle concentrations have been determined for potassium n-octanoate in deuterium oxide over a wide temperature range, 29–123 °C, from the concentration dependence of proton nmr spectral parameters (peak positions, and vicinal splitting values of the α-CH2 multiplet) and carbon-13 nmr chemical shifts. The c.m.c. varies from ca. 0.30 m at ca. 30 °C to ca. 0.50 m at ca. 120 °C and is at a minimum (0.30–0.35 m) in the temperature range ca. 30–50 °C. 23Na+ spin-lattice relaxation times reveal that a co-counterion (Na+) different from that of the surfactant counterion (K+) reflects the micellization process. A second critical micelle concentration has been observed around 1.0 m at ca. 30 °C.

Hydrosulfide-ion dynamics in cesium and rubidium hydrosulfide: a deuteron nuclear magnetic resonance study

1986 ◽  
Vol 64 (7) ◽  
pp. 833-838
Author(s):  
Kenneth R. Jeffrey ◽  
Roderick E. Wasylishen
Keyword(s):  
Quadrupole Interaction ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Site Symmetry ◽  
Time Data ◽  
Molecular Reorientation ◽  
Temperature Range ◽  
Spin Lattice ◽  
Nuclear Quadrupole

RbSD and CsSD have a multiplicity of solid-state phase transitions involving changes in the degree of order of the SD− ion. Because the deuteron has a nuclear quadrupole moment, the observed NMR spectrum reflects any changes that take place in the deuteron-site symmetry as a result of a phase change. Furthermore, the magnitude of the observed nuclear quadrupole interaction depends on the time average of the electric-field gradient at the deuteron site; this, in general, is a function of any molecular motion in the crystal. The nuclear spin–lattice relaxation times provide information about the time scale of any molecular reorientation taking place in the crystal structure. Deuteron NMR spectra and relaxation times are presented for RbSD and CsSD over the temperature range from 100 to 400 K. The spin–lattice relaxation time data show that there is reorientation of the SD− ion in the tetragonal phase of CsSD and in the trigonal phase of RbSD. While the correlation time for the reorientation changes from being short compared with the reciprocal of the quadrupole interaction to being the same order of magnitude in the temperature range studied, the deuterium NMR line shapes do not change substantially. It is concluded that the observed reorientation of the SD− ion in both RbSD and CsSD in the low-temperature noncubic phases is end-for-end flipping of the SD− ion since only reorientation by 180° leaves the static quadrupole splitting unchanged.

NQR Relaxation Studies on Halogenomethyl Groups in Halogenoacetates

1998 ◽  
Vol 53 (6-7) ◽  
pp. 480-483 ◽  
Author(s):  
Maria Zdanowska-Fnjczek
Keyword(s):  
Room Temperature ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Effect Of Temperature ◽  
Relaxation Theory ◽  
Temperature Range ◽  
Spin Lattice ◽  
Relaxation Studies

Abstract The effect of temperature on the chlorine NQR spin-lattice relaxation times in CsH(ClH2-CCOO)2 , KH(Cl3 CCOO) 2 and N(CH3)4 H(ClF2CCOO)2 has been studied in the temperature range 77 K to room temperature. The results were discussed on the basis of NQR relaxation theory.

Molecular Motion in Solid Tetraethyl -and Tetrapropylammonium Tetrafluoroborates

1995 ◽  
Vol 50 (6) ◽  
pp. 584-588 ◽  
Author(s):  
Barbara Szafrańska ◽  
Zdzisław Pająk
Keyword(s):  
Molecular Motion ◽  
Solid Phase ◽  
Complex Cation ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Fluorine Nmr ◽  
Spin Lattice ◽  
Second Moments ◽  
Wide Range

Abstract Proton and fluorine NMR second moments and spin-lattice relaxation times for polycrystalline tetraethyl-and tetrapropylammonium tetrafluoroborates have been measured over a wide range of temperatures. Solid-solid phase transitions were found for both compounds and confirmed by DSC. Methyl group C3 reorientation followed by more complex cation motions was evidenced in the low temperature phases. Overall cation reorientation characterises the high temperature phases of both compounds. Isotropic anion reorientation was found in both salts in both phases.

Application of Adiabatic Rapid Passage Nuclear Magnetic Resonance Techniques to the Study of Molecular Motions in Solids

1974 ◽  
Vol 52 (2) ◽  
pp. 191-197 ◽  
Author(s):  
J. A. Ripmeester ◽  
B. A. Dunell
Keyword(s):  
Molecular Motion ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Adiabatic Rapid Passage ◽  
Spin Lattice ◽  
Second Moments ◽  
New Information ◽  
Rotating Frame Relaxation ◽  
Rapid Passage

The adiabatic rapid passage (ARP) technique was applied to the study of molecular motion in solids. Second moments and spin–lattice relaxation times for solid furan and benzene were derived using ARP methods from 77 °K to the respective melting points. Unusual variations of the ARP signal height and shape with temperature were observed for these solids. These effects were interpreted as being due to the presence of short rotating frame relaxation times. New information regarding molecular motion in solid furan, as well as acetic acid-d1, was obtained. Also some quantitative statements have been made regarding the conditions required to observe an ARP signal in the solid state.

A nuclear magnetic resonance investigation of n -pentane, n -hexane and cyclo pentane

1954 ◽  
Vol 222 (1151) ◽  
pp. 526-541 ◽  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Molecular Motion ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Kcal Mole ◽  
Second Moment ◽  
Spin Lattice ◽  
Second Moments

The nuclear magnetic resonance spectra and spin-lattice relaxation times have been measured for the protons in n -pentane (C 5 H 12 ), n -hexane (C 6 H 14 ) and cyclo pentane (C 5 H 10 ) all in the solid state. The temperature range covered was from 70° K to the melting-points of 143·4° K for n -pentane, 177·8° K for n -hexane and 179·4° K for cyclo pentane. In the case of n -pentane and n -hexane the second moments of the absorption lines were found to be smaller than the computed rigid lattice values over the. whole temperature range. Possible molecular motions which might cause this reduction are discussed. It is suggested that the most probable type of motion is reorientation of the methyl groups at the ends of each molecule about the adjacent C—C bonds. An analysis of the spin-lattice relaxation times shows that this reorientation process is governed by an activation energy of 2·7 kcal/mole for n -pentane and 2·9 kcal/mole for n -hexane, values which support the mechanism postulated. At the lowest temperature the absorption lines had not reached their full widths, even though the reorientation frequencies at these temperatures were considerably less than the line-widths. The experimental second moment for cyclo pentane below about 120° K indicates that the lattice is effectively rigid in this temperature region. The uncertainties in both the experimental and theoretical second moments do not allow a distinction to be drawn between the plane and puckered molecular models. At the temperature of the first transition (122·4° K) the line-width second moment and relaxation time all show a sudden decrease. The low value of second moment at the higher temperatures indicates that considerable molecular motion is occurring, the molecules rotating with spherical symmetry. The change in crystal structure at the temperature of the second transition (138·1° K) is thought to be a direct result of this spherical symmetry. As the temperature increases, the results indicate that more molecular motion must be occurring, and it is thought that the rotating molecules are diffusing through the lattice.

Molecular Reorientation in the Plastic Crystalline Phase of Tris

1979 ◽  
Vol 32 (4) ◽  
pp. 905 ◽  
Author(s):  
RE Wasylishen ◽  
PF Barron ◽  
DM Doddrell
Keyword(s):  
Phase Transition ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Molecular Reorientation ◽  
Liquid Phase Transition ◽  
X Ray ◽  
Spin Lattice

Carbon-13 N.M.R. spectra of tris(hydroxymethyl)aminomethane (Tris) have been measured between 407 and 461 K. Proton-decoupled 13C N.M.R. spectra of solid Tris between 407 K and its melting point are relatively sharp (v� < 30 Hz) indicating rapid overall molecular reorientation in this temperature range. It was not possible to detect a 13C N.M.R, signal for Tris below 407 K. The observed 13C N.M.R. spin-lattice relaxation times appear continuous across the solid ↔ liquid phase transition. From the temperature dependence of T1, a rotational activation energy of 51.6 � 6 kJ mol-1 is calculated, which indicates that the molecules must expend considerable energy in reorienting. The N.M.R. results are discussed in relation to previous differential scanning calorimetry and X-ray diffraction data which indicate that Tris undergoes a solid ↔ solid transition at 407 K.

scholarly journals NMR relaxometry: Spin lattice relaxation times in the laboratory frame versus spin lattice relaxation times in the rotating frame

2010 ◽  
Vol 495 (4-6) ◽  
pp. 287-291 ◽  
Author(s):  
Emilie Steiner ◽  
Mehdi Yemloul ◽  
Laouès Guendouz ◽  
Sébastien Leclerc ◽  
Anthony Robert ◽  
...  
Keyword(s):  
Relaxation Times ◽  
Lattice Relaxation ◽  
Laboratory Frame ◽  
Spin Lattice Relaxation ◽  
Rotating Frame ◽  
Spin Lattice ◽  
Nmr Relaxometry

A study of molecular motion in tetramethylphosphonium halides by proton magnetic resonance

1976 ◽  
Vol 54 (12) ◽  
pp. 1985-1990 ◽  
Author(s):  
T. T. Ang ◽  
B. A. Dunell
Keyword(s):  
Molecular Motion ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
X Ray Diffraction ◽  
Hexagonal Crystal ◽  
Methyl Group ◽  
X Ray ◽  
Spin Lattice ◽  
Second Moments

Spin–lattice relaxation times of tetramethylphosphonium chloride, bromide, and iodide were measured between 100 and 500 K and the two minima in T1 found for each compound have been assigned to methyl group reorientation and whole cation tumbling. The second moments also indicate that the cations are tumbling isotropically at nmr frequencies in the upper half of this temperature range, and suggest that librational oscillation of the whole cation occurs at frequencies at least of the order of 105 s−1 near 150 K. The energy barriers for both methyl group reorientation and isotropic tumbling decrease from chloride to bromide but increase when one goes from bromide to iodide. Powder photograph X-ray diffraction analysis indicates that the chloride and bromide have hexagonal crystal structures (a and c measured), but that the iodide has lower, undetermined symmetry.

A Nuclear Spin Relaxation Study of the Spin–Rotation Interaction in Symmetric Top Molecules

1972 ◽  
Vol 50 (12) ◽  
pp. 1262-1272 ◽  
Author(s):  
Robin L. Armstrong ◽  
James A. Courtney
Keyword(s):  
Relaxation Times ◽  
Lattice Relaxation ◽  
Relaxation Mechanism ◽  
Spin Rotation ◽  
Spin Lattice Relaxation ◽  
Molecular Reorientation ◽  
Effective Spin ◽  
Spin Lattice ◽  
Simple Exponential Function ◽  
Symmetric Top Molecules

The spin–lattice relaxation times T1 of 1H, 19F, and 31P nuclei were measured in gaseous samples of BF3, CHF3, CH3F, PH3, and NH3 at room temperature for densities from 0.03 to 10 amagat. In several cases the behavior of T1 at the lowest densities snowed deviations from the linear variation characteristic of the extreme narrowing region. The spin–rotation interaction provides the dominant relaxation mechanism in all cases. The data are analyzed on the basis of the assumption that the collision modulated spin–rotation interaction may be described by a single correlation function which is a simple exponential function of time. Values of an effective spin–rotation constant and a cross section for molecular reorientation are obtained for each gas. The results obtained are compared with those available from other types of experiments. This comparison indicates that the theory for spin–lattice relaxation in dilute gases of symmetric top molecules needs to be carefully reassessed.

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