Enthalpies of transfer from methanol to acetonitrile, t-butyl alcohol, and aqueous methanol of the reactions and the transition state in the bimolecular substitution of tetraethyltin by mercuric chloride

1969 ◽  
pp. 117a ◽  
Author(s):  
M. H. Abraham ◽  
F. Behbahany ◽  
M. J. Hogarth ◽  
R. J. Irving ◽  
G. F. Johnston
Keyword(s):  
Transition State ◽  
Mercuric Chloride ◽  
Butyl Alcohol ◽  
Aqueous Methanol ◽  
Enthalpies Of Transfer

Solubility and Thermodynamic Transfer Functions of Cesium Dianilinetetraisothiocyanatochromate(III)

1998 ◽  
Vol 63 (3) ◽  
pp. 293-298
Author(s):  
Vladislav Holba
Keyword(s):  
Experimental Data ◽  
Isopropyl Alcohol ◽  
Transfer Functions ◽  
Butyl Alcohol ◽  
Aqueous Methanol ◽  
Gibbs Energies ◽  
Gibbs Energy Of Transfer ◽  
Energy Of Transfer ◽  
The Given ◽  
Reference Electrolyte

The solubilities of cesium dianilinetetraisothiocyanatochromate(III) in water as well as in aqueous methanol, isopropyl alcohol, tert-butyl alcohol and acetonitrile were measured as a function of temperature and solvent composition. The Gibbs energies, enthalpies and entropies of transfer of the salt from water to the given solvents have been evaluated from experimental data. The contribution of [Cr(C6H5NH2)2(NCS)4]- ion to the Gibbs energy of transfer of the investigated salt has been calculated using the tetraphenylarsonium tetraphenylborate (TATB) reference electrolyte assumption.

Transfer Thermodynamic Functions ∆Gt0, ∆Ht0 and T∆St0 of cis- and trans-[CoCl2(en)2]+ Isomers in Aqueous Mixtures of Methanol, tert-Butyl Alcohol and Acetonitrile

2000 ◽  
Vol 65 (9) ◽  
pp. 1455-1463
Author(s):  
Oľga Vollárová ◽  
Ján Benko
Keyword(s):  
Enthalpy Of Solution ◽  
Transfer Functions ◽  
Partial Molar Volumes ◽  
Butyl Alcohol ◽  
Aqueous Mixtures ◽  
Aqueous Methanol ◽  
Solvent Interactions ◽  
Tert Butyl Alcohol ◽  
Surface Charge Distribution ◽  
Cis And Trans

The solubility, partial molar volume and standard integral molar enthalpy of solution of cis- and trans-[CoCl2(en)2]Cl in water, aqueous methanol, aqueous tert-butyl alcohol and aqueous acetonitrile are reported. The transfer functions ∆Gt0, ∆Ht0 and T∆St0 as well as partial molar volumes are used to obtain information on the solute-solvent interactions. Results obtained are discussed in terms of differences in the surface charge distribution in isomeric coordination species.

Nucleophilic cleavage of diaryl disulphides

1973 ◽  
Vol 26 (1) ◽  
pp. 121 ◽  
Author(s):  
DAR Happer ◽  
JW Mitchell ◽  
GJ Wright
Keyword(s):  
Transition State ◽  
Reaction Rate ◽  
Substituent Effects ◽  
Butyl Alcohol ◽  
Sulphur Atom ◽  
Cyanide Ion ◽  
Benzene Rings ◽  
Nucleophilic Cleavage ◽  
Rapid Equilibrium ◽  
Electron Withdrawal

The rates of cleavage of 14 symmetrically substituted diaryl disulphides by cyanide ion have been measured in 60% aqueous t-butyl alcohol at pH 9.2. A plot of log k against σ� shows that while the reaction rate is accelerated by inductive electron withdrawal from the benzene rings, substituents capable of conjugative interaction are not correlated by their σ� parameters. +R substituents cause reaction to occur much faster than predicted on the basis of their σ� values, while -R substituents react more slowly than predicted. Measurement of rates of cleavage of three series of unsymmetrically substituted disulphides by cyanide or hydroxide shows that these unusual substituent effects arise from substituents in the thiocyanate-forming aryl ring. This behaviour is explained in terms of a change in the electronic behaviour of the thio- cyanate-forming sulphur atom from -I, + R in the disulphide to -I,-R in the rate-determining transition state for the reaction. The study does not show whether the cleavage involves an SN2 process or rapid equilibrium formation of a pentacovalent intermediate.

Initial state and transition state contributions to solvent effects on activation enthalpies for substitution reactions of tris(1,10-phenanthroline)iron(II) in aqueous methanol

1983 ◽  
Vol 8 (3) ◽  
pp. 148-152 ◽  
Author(s):  
Michael J. Blandamer ◽  
John Burgess ◽  
Timothy Digman ◽  
Philip P. Duce ◽  
John P. McCann ◽  
...  
Keyword(s):  
Transition State ◽  
Solvent Effects ◽  
Aqueous Methanol ◽  
Substitution Reactions ◽  
Initial State
Sign in / Sign up

Export Citation Format

Share Document