Anilinium chloride as a model for the transition state for benzyl chloride solvolysis

1969 ◽  
Vol 47 (8) ◽  
pp. 1437-1439 ◽  
Author(s):  
Ikchoon Lee ◽  
J. B. Hyne
Keyword(s):  
Transition State ◽  
Benzyl Chloride ◽  
Composition Dependence ◽  
Structural Model ◽  
Activation Process ◽  
Electrostatic Model ◽  
Partial Molal Volume ◽  
Tetraethylammonium Chloride ◽  
Molal Volume ◽  
Alkyl Ammonium

The solvent composition dependence of the partial molal volume of the transition state of benzyl chloride solvolysing in water–ethanol mixtures is compared with that of anilinium chloride and a number of quaternary alkyl ammonium chlorides. It is concluded that anilinium chloride is not a good electrostatic model for the benzyl chloride transition state even though it may be a fair structural model. The partial molal volume of tetraethylammonium chloride is very similar to that of the transition state suggesting that charge development in the activation process is far from being fully ionic.

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.

Effect of Pressure on the Solvolysis of Dimethyl-t-butyl Sulfonium Iodide in Ethanol–Water Mixtures

1972 ◽  
Vol 50 (14) ◽  
pp. 2270-2275 ◽  
Author(s):  
Claude S. Davis ◽  
J. B. Hyne
Keyword(s):  
Reaction Mechanism ◽  
Transition State ◽  
Pressure Dependence ◽  
Composition Dependence ◽  
Partial Molal Volume ◽  
Molal Volume ◽  
Effect Of Pressure ◽  
Partial Molal Volumes ◽  
Molal Volumes

The pressure dependence of the rate of solvolysis of dimethyl-t-butyl sulfonium iodide has been studied in ethanol–water mixtures at 60.00 °C. Determination of the partial molal volume of the substrate ions has enabled the volumes of activation to be dissected into initial and transition state components. The solvent composition dependence of the partial molal volumes of the two states provides further details of the nature of the reaction mechanism.

scholarly journals INTERACTION STUDIES OF AMINO ACIDS IN AQUEOUS SODIUM BROMIDE SOLUTIONS AT DIFFERENT TEMPERATURE

2017 ◽  
Vol 5 (10) ◽  
pp. 160-167
Author(s):  
Yasmin Akhtar
Keyword(s):  
Amino Acids ◽  
Infinite Dilution ◽  
Adiabatic Compressibility ◽  
Sodium Bromide ◽  
Apparent Molal Volume ◽  
Partial Molal Volume ◽  
Molal Volume ◽  
Solvent Interactions ◽  
Aqueous Sodium ◽  
Bonding Effect

Densities, ultrasonic velocities and viscosities of L- Valine and L- Phenylalanine in aqueous sodium bromide (0.00, 0.025 and 0.05) m solutions have been determined experimentally at 308 and 313 K. The results obtained from density ultrasonic velocity and viscosity measurement have been used to calculate the apparent molal volume, фv, apparent molal, adiabatic compressibility ф Ks, partial molal volume ф0v at infinite dilution, partial molal adiabatic compressibility ф0Ks at infinite dilution, transfer volume ∆ф(tr), experimental slopes Sv and SKs,Falkenhagen coefficient A and  Jones-Dole B coefficient. The results are discussed in terms of the dehydration effect of the sodium bromide upon the amino acids and weak solute- solute and strong solute- solvent interactions. The properties of these amino acids in water and water + sodium bromide solution systems are discussed in terms of the charge, size and hydrogen bonding effect.

scholarly journals Study of Physical Properties for Sodium acetate with Water and Water - Acetone mixtures at Different Temperatures

2017 ◽  
Vol 27 (4) ◽  
Author(s):  
Ahmed Mohammed Abbas ◽  
Zainab Wajdi Ahmed ◽  
Alaa Fadhil Sulaiman ◽  
Issam AbdalKreem AbdalLatif
Keyword(s):  
Sodium Acetate ◽  
Apparent Molal Volume ◽  
Viscosity Data ◽  
Partial Molal Volume ◽  
Molal Volume ◽  
Solvent Interactions ◽  
Acetone Water ◽  
Thermodynamic Activation Parameter ◽  
Different Temperatures ◽  
Apparent Molal Compressibility

In this study binary and ternary solutions are prepared by using the sodium acetate concentrations (0.1, 0.125, 0.2, 0.25, 0.4, 0.5, 0.8, 1 M) in water and acetone –water mixtures .The important parameters such as apparent molal volume, the partial molal volume transfer,  apparent  molal compressibility, free energy of activation of viscous flow and thermodynamic activation parameter (enthalpy and entropy) determined of sodium acetate in water , 20%, 40% ,60% and 80% V/V acetone –water mixtures at 298.15K, 303.15K, and 308.15K from density and viscosity measurements espectively. The limiting apparent molal volumes and experimental slopes were derived from the Masson equation, have been interpreted in terms of solute–solvent and solute–solute interactions  respectively. The viscosity data were analyzed using theJones–Dole equation and the derived parameter B - coefficient has also been interpreted in terms of solute–solvent interactions in the solutions. 

An Yttrium Hydride-Silane Complex as a Structural Model for a σ-Bond Metathesis Transition State

2013 ◽  
Vol 125 (15) ◽  
pp. 4337-4340 ◽  
Author(s):  
Jiliang Zhou ◽  
Jiaxiang Chu ◽  
Yanyan Zhang ◽  
Guang Yang ◽  
Xuebing Leng ◽  
...  
Keyword(s):  
Transition State ◽  
Structural Model ◽  
Yttrium Hydride

Solvent-induced stresses in glassy polymer: Elastic model

1999 ◽  
Vol 14 (10) ◽  
pp. 4111-4118 ◽  
Author(s):  
Wei-Lung Wang ◽  
J. R. Chen ◽  
Sanboh Lee
Keyword(s):  
Mass Transport ◽  
Surface Concentration ◽  
Anomalous Transport ◽  
Initial Time ◽  
Elastic Model ◽  
Partial Molal Volume ◽  
Longitudinal Displacement ◽  
Linear Elasticity Theory ◽  
Molal Volume ◽  
Induced Stresses

The solvent-induced stresses in glassy polymers were investigated. The mass transport accounts for case I, case II, and anomalous transport. Case I transport is attributed to the concentration gradient, whereas case II transport is attributed to stress relaxation. Anomalous transport is the mixture of case I and case II. Both one-side and two-side mass transports with the boundary condition of constant surface concentration are considered. The stresses and longitudinal displacement arising from the mass transport are formulated based on the linear elasticity theory. The maximum stress is always located at the surface at the initial time. The stresses are a function of the partial molal volume, Young's modulus, and Poisson's ratio. From the longitudinal displacement data, the partial molal volume was determined.

Cubic Mesophase in an Unsymmetrical Alkyl Ammonium Salt. Synthesis and Structural Model

ChemPhysChem ◽  
2002 ◽  
Vol 3 (12) ◽  
pp. 1024-1030 ◽  
Author(s):  
Corinne Soulié ◽  
Pierre Bassoul ◽  
François Tournilhac
Keyword(s):  
Ammonium Salt ◽  
Structural Model ◽  
Alkyl Ammonium

Heat capacities and volumes of some non-electrolytes in N,N-dimethylformamide at 298.15 K

1987 ◽  
Vol 65 (12) ◽  
pp. 2810-2814 ◽  
Author(s):  
Henryk Piekarski
Keyword(s):  
Ethylene Glycol ◽  
Heat Capacities ◽  
Scaled Particle Theory ◽  
Partial Molal Volume ◽  
Cavity Formation ◽  
Particle Theory ◽  
Molal Volume ◽  
Analogous Data ◽  
Other Substances ◽  
Apparent Molal Heat Capacities

Heat capacities and densities of dilute solutions of formamide, acetone, tetrahydrofuran, ethylene glycol, 2-methoxyethanol, and 2-ethoxyethanol in N,N-dimethylformamide were determined at 298.15 K. Apparent molal heat capacities and volumes for these solutes in DMF were calculated and compared with the analogous data for other substances in DMF solution as well as with the data concerning solutions in methanol and water. Heat capacities of cavity formation (ΔCcav) in DMF were calculated on the basis of the Scaled Particle Theory. ΔCcav appeared to be linearly correlated with the standard partial molal volume of corresponding solutes in DMF. Similar dependences were also found for aqueous and methanolic solutions of the non-electrolytes.

scholarly journals Asymmetric Cyanation of Activated Olefins with Ethyl Cyanoformate Catalyzed by Ti(IV)-Catalyst: A Theoretical Study

Catalysts ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 1079
Author(s):  
Zhishan Su ◽  
Changwei Hu ◽  
Nasir Shahzad ◽  
Chan Kyung Kim
Keyword(s):  
Transition State ◽  
Self Assembly ◽  
Theoretical Study ◽  
Activation Barrier ◽  
Cinchona Alkaloid ◽  
Activation Process ◽  
Construction Step ◽  
Dual Activation ◽  
Membered Transition State ◽  
Step Mechanism

The reaction mechanism and origin of asymmetric induction for conjugate addition of cyanide to the C=C bond of olefin were investigated at the B3LYP-D3(BJ)/6-31+G**//B3LYP-D3(BJ)/6-31G**(SMD, toluene) theoretical level. The release of HCN from the reaction of ethyl cyanoformate (CNCOOEt) and isopropanol (HOiPr) was catalyzed by cinchona alkaloid catalyst. The cyanation reaction of olefin proceeded through a two-step mechanism, in which the C-C bond construction was followed by H-transfer to generate a cyanide adduct. For non-catalytic reaction, the activation barrier for the rate-determining C-H bond construction step was 34.2 kcal mol−1, via a four-membered transition state. The self-assembly Ti(IV)-catalyst from tetraisopropyl titanate, (R)-3,3′-disubstituted biphenol, and cinchonidine accelerated the addition of cyanide to the C=C double bond by a dual activation process, in which titanium cation acted as a Lewis acid to activate the olefin and HNC was orientated by hydrogen bonding. The steric repulsion between the 9-phenanthryl at the 3,3′-position in the biphenol ligand and the Ph group in olefin raised the Pauli energy (ΔE≠Pauli) of reacting fragments at the re-face attack transition state, leading to the predominant R-product.

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