Temperature Dependence of Activation Volumes of Solvolysis Reactions in Light and Heavy Water

1973 ◽  
Vol 51 (11) ◽  
pp. 1687-1692 ◽  
Author(s):  
Claude S. Davis ◽  
J. B. Hyne
Keyword(s):  
Temperature Dependence ◽  
Heavy Water ◽  
Pressure Dependence ◽  
Benzyl Chloride ◽  
Methanesulfonyl Chloride ◽  
Extensive Data

The pressure dependence of the solvolysis rates for benzyl chloride, isopropyl bromide, and methanesulfonyl chloride in H2O and D2O have been measured. The temperature dependence of the activation volumes appears to be indicative of the mechanism of solvolyses and the differences in the temperature dependence of the activation volumes for the two solvents are consistent with D2O being the more structured. The more extensive data in the case of methanesulfonyl chloride deuterolysis indicates extremum behavior in ΔV* as a function of temperature in the 5–25 °C range.

Heat capacity of activation for the hydrolysis of methanesulfonyl chloride and benzenesulfonyl chloride in light and heavy water

1969 ◽  
Vol 47 (22) ◽  
pp. 4199-4206 ◽  
Author(s):  
R. E. Robertson ◽  
B. Rossall ◽  
S. E. Sugamori ◽  
L. Treindl
Keyword(s):  
Heat Capacity ◽  
Free Energy ◽  
Temperature Dependence ◽  
Heavy Water ◽  
Bond Formation ◽  
Sulfonyl Chlorides ◽  
Benzenesulfonyl Chloride ◽  
Methanesulfonyl Chloride ◽  
Hydrolysis Of ◽  
Parameter Temperature Dependence

Rates of solvolysis of methanesulfonyl chloride and benzenesulfonyl chloride have been determined in H2O and D2O. The free energy, enthalpy, entropy, and heat capacity of activation were calculated. The exceptional accuracy of the data permitted an estimation of dΔCp≠/dT from a four parameter temperature dependence of the kinetic rates.From these data we conclude that both sulfonyl chlorides hydrolyse by the same mechanism (Sn2) The change in R from CH3 to C6H5 in RSO2Cl did not alter ΔCp≠ but ΔS≠ (20°) was changed from −8.32 to −13.25 cal deg−1 mole−1, respectively. The significance of this difference is attributed to the probability of bond formation rather than to differences in solvent reorganization.

Temperature Dependence of the Intervalley Deformation Potential of GaAs/AlAs Superlattices Under Hydrostatic Pressure

1997 ◽  
Vol 499 ◽  
Author(s):  
S. Guha ◽  
Q. Cai ◽  
M. Chandrasekhar ◽  
H. R. Chandrasekhar ◽  
Hyunjung Kim ◽  
...  
Keyword(s):  
Hydrostatic Pressure ◽  
Temperature Dependence ◽  
Pressure Dependence ◽  
Type I ◽  
Type Ii ◽  
Deformation Potential ◽  
Intervalley Scattering

ABSTRACTWe have studied the pressure dependence of the type-I and type-II transitions in (GaAs)m/(AlAs)m superlattices by photoluminescence (PL) spectroscopy. From the study of PL linewidths of the type-I exciton as a function of pressure and temperature, we determine the intervalley deformation potential. Beyond the type-I and type-II crossover, the PL linewidth increases both as a function of pressure and temperature. We find that the electron-phonon deformation potential for Γ-X intervalley scattering varies with temperature.

Temperature Dependence of N2-Relaxation of Rotational Lines of Propionitrile

1992 ◽  
Vol 47 (9) ◽  
pp. 999-1002 ◽  
Author(s):  
H.-W. Nicolaisen ◽  
H. Mäder ◽  
F. Rohart
Keyword(s):  
Temperature Dependence ◽  
Pressure Dependence ◽  
Decay Rates ◽  
Rotational Relaxation ◽  
Pressure Broadening ◽  
Ambient Temperatures

AbstractThe temperature dependence of the rotational relaxation of propionitrile, CH3CH2C15N, has been investigated by means of microwave transient emission signals. From analysis of the pressure dependence of the coherence decay rates for the rotational lines (J, K-, K+) = (2, 0, 2)-(3, 0, 3), (2,1, 2)-(3, 1, 3), and (2, 2, l)-(3, 2, 2) pressure broadening parameters have been derived for mixtures with nitrogen in the 210-300 K range and for the pure gas at ambient temperatures

Temperature dependence and pressure dependence of the vibrational properties of corannulene

2008 ◽  
Vol 245 (10) ◽  
pp. 2261-2263 ◽  
Author(s):  
Laurent Alvarez ◽  
Rozenn Le Parc ◽  
Vincent Jourdain ◽  
Samuel Dennler ◽  
Jean Louis Bantignies ◽  
...  
Keyword(s):  
Temperature Dependence ◽  
Pressure Dependence ◽  
Vibrational Properties

Interaction between argon atoms

1960 ◽  
Vol 255 (1283) ◽  
pp. 456-476 ◽  
Keyword(s):  
Temperature Dependence ◽  
Interaction Energy ◽  
High Temperatures ◽  
Pressure Dependence ◽  
Virial Coefficient ◽  
Second Virial Coefficient

The interaction energy between argon atoms is correlated with the following experimental properties of argon: (1) the temperature dependence of the entropy of the crystal, (2) the temperature dependence of the energy of the crystal, (3) the temperature dependence of the density of the crystal, (4) the pressure dependence of the density of the crystal, (5) the temperature dependence of the second virial coefficient of the gas, (6) the viscosity at high temperatures of the gas. The interaction energy which best accords with all these properties is strikingly different from the commonly advocated difference between an inverse twelfth power and an inverse sixth power of the distance.

Pressure- and Temperature-Dependence of the Electrical Resistivity of Some Nonmagnetic d-electron Amorphous Alloys

1982 ◽  
Vol 37 (11) ◽  
pp. 1235-1240
Author(s):  
G. Fritsch ◽  
J. Wilier ◽  
E. Lüscher
Keyword(s):  
Electrical Resistivity ◽  
Temperature Dependence ◽  
Pressure Dependence ◽  
Amorphous Alloys ◽  
Electron Gas ◽  
Temperature Dependent ◽  
Absolute Value ◽  
Volume Dependence ◽  
Dependent Term ◽  
Scattering Potential

Using the Ziman-formulation a model is derived which describes the pressure dependence of the electrical resistivity of d-electron amorphous alloys. It is shown how the volume dependence of the scattering-potential, electron-gas-properties and the Grüneisenparameter determine the P-dependence of a constant and a temperature dependent term in the resistivity. The absolute value of the resistivity is discussed.

scholarly journals Anomalous Temperature Dependence of NQR Frequencies

1990 ◽  
Vol 45 (3-4) ◽  
pp. 449-458
Author(s):  
R. J. C. Brown
Keyword(s):  
Heat Capacity ◽  
Temperature Dependence ◽  
Elastic Constants ◽  
Pressure Dependence ◽  
Anomalous Temperature Dependence ◽  
Anomalous Temperature ◽  
Reorientational Motion ◽  
Successes And Failures

Abstract The anomalous temperature dependence of NQR frequencies which is often observed in crystals in which there is reorientational motion of ions or molecules is considered. Two theories of the phenomena, the jump rotation theory and the pseudo-spin theory, are described, and their successes and failures are discussed. The importance of considering other properties such as pressure dependence of NQR, heat capacity, and elastic constants is emphasized, and it is shown that neither theory is entirely satisfactory at present.

scholarly journals The Pressure Dependence of Self Diffusion in Supercooled Light and Heavy Water

1988 ◽  
Vol 92 (10) ◽  
pp. 1111-1117 ◽  
Author(s):  
F. X. Prielmeier ◽  
E. W. Lang ◽  
R. J. Speedy ◽  
H.-D. Lüdemann
Keyword(s):  
Heavy Water ◽  
Pressure Dependence ◽  
Self Diffusion

ON THE PRESSURE DEPENDENCE OF REACTION RATES

1966 ◽  
Vol 44 (18) ◽  
pp. 2193-2203 ◽  
Author(s):  
H. S. Golinkin ◽  
W. G. Laidlaw ◽  
J. B. Hyne
Keyword(s):  
Pressure Dependence ◽  
Benzyl Chloride ◽  
Activation Volume ◽  
Functional Dependence ◽  
Quadratic Function ◽  
Activation Parameters ◽  
Reaction Rates ◽  
General Applicability ◽  
Order Polynomial ◽  
Derivatives Of

The functional dependence of the rate constant for benzyl chloride solvolysis on pressure is investigated with a view to obtaining reliable values of the activation parameters. It is concluded that a second order polynomial is the best description of this system, reproducing the experimental data with a greater degree of precision than the other published functions. A method for determining the precision of the derivatives of the logarithmic rate is presented, and the pressure dependence of the activation volume is demonstrated. Various systems from the literature are analyzed to demonstrate the general applicability of the quadratic function.

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