The Initial-State Contribution to the Activation Volume for Benzyl Chloride Solvolysis

1967 ◽  
Vol 89 (6) ◽  
pp. 1307-1312 ◽  
Author(s):  
H. S. Golinkin ◽  
Ikchoon. Lee ◽  
J. B. Hyne
Keyword(s):  
Benzyl Chloride ◽  
Activation Volume ◽  
Initial State ◽  
State Contribution

The pressure dependence of benzyl chloride solvolysis in aqueous acetone and aqueous dimethylsulfoxide

1970 ◽  
Vol 48 (16) ◽  
pp. 2494-2499 ◽  
Author(s):  
Digby D. Macdonald ◽  
J. B. Hyne
Keyword(s):  
Transition State ◽  
Benzyl Chloride ◽  
Activation Volume ◽  
Aqueous Acetone ◽  
Solvent Composition ◽  
Pressure Data ◽  
Initial State ◽  
First Order ◽  
Solvent Systems ◽  
Aqueous Dimethylsulfoxide

First-order rate constants for the solvolysis of benzyl chloride in a series of aqueous acetone and aqueous dimethylsulfoxide (DMSO) mixtures at 50.100 °C and at various pressures in the range 1–4083 atm are reported. Volume of activation, calculated from the rate/pressure data, is found to exhibit extremum behavior with varying solvent composition in both solvent systems. The activation volumes are dissected into their initial state and transition state contributions by determining the "instantaneous" volumes of solution of benzyl chloride in the solvent systems. The contributions of both the initial state and the transition state to the behavior of the activation volume as a function of solvent composition are discussed.

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.

Transition state volumes and solvolysis mechanisms

1970 ◽  
Vol 48 (13) ◽  
pp. 2025-2030 ◽  
Author(s):  
MOYRA J. Mackinnon ◽  
A. B. Lateef ◽  
J. B. Hyne
Keyword(s):  
Transition State ◽  
Benzyl Chloride ◽  
Activation Volume ◽  
Solvent Composition ◽  
Binary Solvent ◽  
Partial Molal Volume ◽  
Butyl Chloride ◽  
Molal Volume ◽  
Reaction Type

The transition state partial molal volume behavior, [Formula: see text] as a function of binary solvent composition was obtained for three reactions by dissection of the activation volume, ΔV*, into initial and transition state components: [Formula: see text] The solvolyses of t-butyl chloride, benzyl chloride, and p-chlorobenzyl chloride represented a gradation of reaction type between SN1 and SN2 and the transition state partial molal volume behavior was found to be distinctly different in each case and in agreement with the mechanistic classification of these reactions.

Tensile Failure of 55-Nitinol Wire

1975 ◽  
Vol 33 ◽  
pp. 46-47
Author(s):  
F. I. Grace
Keyword(s):  
Shape Memory ◽  
Shape Memory Effect ◽  
Memory Effect ◽  
Stoichiometric Composition ◽  
Tensile Failure ◽  
Initial State ◽  
Initial Shape ◽  
Nitinol Wire ◽  
Cscl Type ◽  
Shear Transformation

An interest in NiTi alloys with near stoichiometric composition (55 NiTi) has intensified since they were found to exhibit a unique mechanical shape memory effect at the Naval Ordnance Laboratory some twelve years ago (thus refered to as NITINOL alloys). Since then, the microstructural mechanisms associated with the shape memory effect have been investigated and several interesting engineering applications have appeared.The shape memory effect implies that the alloy deformed from an initial shape will spontaneously return to that initial state upon heating. This behavior is reported to be related to a diffusionless shear transformation which takes place between similar but slightly different CsCl type structures.

The Initial State of Man in Augustine's De genesi contra Manichaeos

2002 ◽  
Vol 42 (1-4) ◽  
pp. 195-202
Author(s):  
György Heidl
Keyword(s):  
Initial State

Comparative study of the impact of two mechanical perforation densities on the behavior of a sandy soil

2012 ◽  
Vol 8 (1) ◽  
pp. 37-48
Author(s):  
S. Chehaibi ◽  
K. Abrougui ◽  
F. Haouala
Keyword(s):  
Soil Water ◽  
Sandy Soil ◽  
Water Infiltration ◽  
Cone Penetration ◽  
Initial State ◽  
Soil Water Infiltration ◽  
Good Improvement ◽  
The Impact ◽  
Positive Effect ◽  
Resistance To Penetration

The effects of mechanical perforation densities by extracting soil cores through an aerator Vertidrain with a working width of 1.6 m and equipped with hollow tines spaced of 65 mm, were studied on a sandy soil of a grassy sward in the Golf Course El Kantaoui in Sousse (Tunisia). The mechanical aeration was performed at two densities: 250 and 350 holes/m2. The cone penetration resistance and soil water infiltration were measured. These parameters were performed at initial state before aeration (E0) and then on the 10th, 20th and 30th day after aeration. These results showed that perforation density of 350 holes/m2 had a positive effect on the soil by reducing its cone resistance to penetration compared to the initial state (Rp = 14.8 daN/cm2). At 5 cm depth the decrease in resistance to penetration was 34% and 43% on the 10th and 20th day after aeration, respectively. However, on the 30th day after aeration the soil resistance to penetration tended to grow and its value compared to the initial state decreased only by 21 and 26%, respectively, at 5 and 15 cm of depth only by 10% and 9% with 250 holes/m2 density. The soil water infiltration made a good improvement after aeration compared to the initial state. This parameter increased from 4.8 cm/h to 8.3, 10.9 and 13.1 cm/h with 250 holes/m2 density and to 10, 12.9 and 14.8 cm/h with 350 holes/m2 density on the 10th, 20th and 30th day following the aeration.

Basic set of experiments for determination of mechanical properties of sand

2014 ◽  
Vol 62 (1) ◽  
pp. 129-137
Author(s):  
A. Sawicki ◽  
J. Mierczyński
Keyword(s):  
Mechanical Properties ◽  
Soil Mechanics ◽  
Physical And Mechanical Properties ◽  
Local Strain ◽  
Initial State ◽  
Laboratory Equipment ◽  
Additional Information ◽  
Basic Set ◽  
Initial Anisotropy

Abstract A basic set of experiments for the determination of mechanical properties of sands is described. This includes the determination of basic physical and mechanical properties, as conventionally applied in soil mechanics, as well as some additional experiments, which provide further information on mechanical properties of granular soils. These additional experiments allow for determination of steady state and instability lines, stress-strain relations for isotropic loading and pure shearing, and simple cyclic shearing tests. Unconventional oedometric experiments are also presented. Necessary laboratory equipment is described, which includes a triaxial apparatus equipped with local strain gauges, an oedometer capable of measuring lateral stresses and a simple cyclic shearing apparatus. The above experiments provide additional information on soil’s properties, which is useful in studying the following phenomena: pre-failure deformations of sand including cyclic loading compaction, pore-pressure generation and liquefaction, both static and caused by cyclic loadings, the effect of sand initial anisotropy and various instabilities. An important feature of the experiments described is that they make it possible to determine the initial state of sand, defined as either contractive or dilative. Experimental results for the “Gdynia” model sand are shown.

Photoinduced Charge Transfer Dynamics in Carotenoid-Porphyrin-C60 Triad via the Linearized Semiclassical Nonequilibrium Fermi's Golden Rule

2020 ◽  
Author(s):  
Zhengqing Tong ◽  
Margaret S. Cheung ◽  
Barry D. Dunietz ◽  
Eitan Geva ◽  
Xiang Sun
Keyword(s):  
Charge Transfer ◽  
Golden Rule ◽  
Time Dependent ◽  
Rate Coefficients ◽  
Initial State ◽  
Photoinduced Charge Transfer ◽  
Transfer Rates ◽  
Fermi's Golden Rule ◽  
Photoinduced Charge ◽  
Fermi’S Golden Rule

The nonequilibrium Fermi’s golden rule (NE-FGR) describes the time-dependent rate coefficient for electronic transitions, when the nuclear degrees of freedom start out in a <i>nonequilibrium</i> state. In this letter, the linearized semiclassical (LSC) approximation of the NE-FGR is used to calculate the photoinduced charge transfer rates in the carotenoid-porphyrin-C<sub>60</sub> molecular triad dissolved in explicit tetrahydrofuran. The initial nonequilibrium state corresponds to impulsive photoexcitation from the equilibrated ground-state to the ππ* state, and the porphyrin-to-C<sub>60</sub> and the carotenoid-to-C<sub>60</sub> charge transfer rates are calculated. Our results show that accounting for the nonequilibrium nature of the initial state significantly enhances the transition rate of the porphyrin-to-C<sub>60</sub> CT process. We also derive the instantaneous Marcus theory (IMT) from LSC NE-FGR, which casts the CT rate coefficients in terms of a Marcus-like expression, with explicitly time-dependent reorganization energy and reaction free energy. IMT is found to reproduce the CT rates in the system under consideration remarkably well.

Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte Na3PS4

2020 ◽  
Author(s):  
Theodosios Famprikis ◽  
O. Ulas Kudu ◽  
James Dawson ◽  
Pieremanuele Canepa ◽  
François Fauth ◽  
...  
Keyword(s):  
Ionic Conductivity ◽  
Mechanochemical Synthesis ◽  
Activation Volume ◽  
External Pressure ◽  
Sodium Ion ◽  
Variable Pressure ◽  
Ion Conductor ◽  
Ceramic Synthesis ◽  
Solid State Batteries ◽  
Fast Ion

<div> <p>Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na<sub>3</sub>PS<sub>4</sub> are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg, pair distribution function), spectroscopy (impedance, Raman, NMR, INS) and <i>ab-initio</i> simulations aimed at elucidating the synthesis-property relationships in Na<sub>3</sub>PS<sub>4</sub>. We consolidate previously reported interpretations about the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na<sup>+</sup> migration in Na<sub>3</sub>PS<sub>4</sub>, which is ~30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na<sub>3</sub>PS<sub>4</sub> to ~10<sup>-4</sup> S/cm can be reproduced by applying external pressure on a sample from conventional high temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain and activation volume.</p> </div>

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