The Pseudo Thermodynamics of Solvolysis. A Detailed Study of the Pressure and Temperature Dependence of Benzyl Chloride Solvolysis in <i>t</i>-Butyl Alcohol – Water Mixtures

Dickson, Stuart; Hyne, J. B.

doi:10.1139/v71-391

Cited by 20 publications

(7 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the terminology of Nemethy and Scheraga (19) the presence of the non-electrolvte caused a shift in the waterwater equilibrium toward a greater degree of hydrogen bonding. This extended quasi-aqueous structure is sensitive to changes in temperature (2,20) and pressure (21). It is the former characteristic which is of interest here.…”

Section: Resultsmentioning

confidence: 92%

The Hydrolysis of t-Butyl Chloride in Aquo-Organic Mixtures: Heat Capacity of Activation and Solvent Structure

Robertson¹,

Sugamori²

1972

Can. J. Chem.

View full text Add to dashboard Cite

The temperature dependence of the rate of solvolysis of t-butyl chloride in mixtures of tetrahydrofuran and of acetonitrile in water have been determined. In the high-water range both minor co-solvents lead t o a reduction in the value ofAHf similar to that found previously where alcohol was the co-solvent. However, a remarkable difference in the values of A C~ across the same concentration range reflected a difference in the effect of these two co-solvents on the structural properties of the several solvent media. Where tetrahydrofuran or alcohols are the mirior co-solvent, AC,f becomes much more negative until that concentration is reached where the quasi-aqueous structure collapses. Where acetonitrile is the minor co-solvent A C~ becomes more positive relative to the value found for hydrolysis in water until a value of about -40 cal deg-' mol-' is reached. The implication of these findings concerning the nature of solvation of weakly polar solutes in such mixtures is discussed.On a determine I'influence de la temperature sur la solvolyse du chlorure de r-butyl dans des melanges de tetrahydrofuranne et d'acetonitrile dans l'eau. Dans le domaine de haute concentration en eau, les deux co-solvants mineurs menent a une rtduction de la valeur de AH+ semblable a celle qu'on a trouve precedemment, ou I'alcool Ctait le co-solvant. Toutefois, une difference remarquable dans les valeurs de A C ,~ dans le meme domaine de concentration reflete une difference de I'effet de ces deux co-solvants sur les proprittes structurales des differents milieux de solvants. Lorsque la tttrahydrofuranne ou les alcools sont le co-solvant mineur, A C~ devient beaucoup plus negatifjusqu'a ce qu'on atteigne la concentration ou la structure quasi-aqueuse s'effondre. Lorsque l'acetonitrile est le co-solvant mineur, A C~ devient plus positif comparativement a la valeur qu'on trouve pour I'hydrolyse dans I'eau, jusqu'a ce qu'on atteigne une valeur d'environ -40 cal deg-' mol-I. On discute de I'implication de ces rtsultats relativement a la nature de la solvatation des solutes faiblement polaires dans de tels melanges.

show abstract

Section: Resultsmentioning

confidence: 92%

The Hydrolysis of t-Butyl Chloride in Aquo-Organic Mixtures: Heat Capacity of Activation and Solvent Structure

Robertson¹,

Sugamori²

1972

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…(3) (4) (5) the equations reveals some interesting details. If, for example, Kx > 1.0, then as Kx increases so AH® -» AH2®.…”

Section: A Chemical Equilibriamentioning

confidence: 99%

“…Similarly we can define a quantity A/3®(diff), eq 5. The A/8e(diff) = (AVxe)2Kx/(RT[l + Kx]) (5) possibility that the same set of data can be described by using either model I or II raises new considerations. We outline just two aspects which warrant attention.…”

Section: A Chemical Equilibriamentioning

confidence: 99%

Dependence of equilibrium and rate constants on temperature and pressure

Blandamer¹,

Burgess²,

Robertson³

et al. 1982

Chem. Rev.

View full text Add to dashboard Cite

“…The type of cells used has been described previously (15). Thc conductance measurement was carried out with an automatic conductance bridge General Radio Type 1680-A (1 kHz) which printed the results in 4 to 5 digit integers with all average change of 1000 integer units per half-life measured.…”

Section: Rote Meosrrre~ile~ltsmentioning

confidence: 99%

The volume of activation for benzyl chloride hydrolysis and its pressure dependence

Lohmüller¹,

Macdonald²,

Mackinnon³

et al. 1978

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

Various equations which have been proposed to provide the 'best' functional form for the dependence of rate upon pressure for reactions in solution have been tested for the extraction of ΔV≠ and dΔV≠/dp for the hydrolysis of benzyl chloride at 30 °C and at pressures over the range 1 to 6895 bar. One hundred individual rate constants were determined for this reaction at pressure increments of 345 bar and provide a sufficiently large body of data to permit application of statistical methods for testing the various rate–pressure functions with little risk of bias.

show abstract

The Pseudo Thermodynamics of Solvolysis. A Detailed Study of the Pressure and Temperature Dependence of Benzyl Chloride Solvolysis in t-Butyl Alcohol – Water Mixtures

Cited by 20 publications

References 8 publications

The Hydrolysis of t-Butyl Chloride in Aquo-Organic Mixtures: Heat Capacity of Activation and Solvent Structure

The Hydrolysis of t-Butyl Chloride in Aquo-Organic Mixtures: Heat Capacity of Activation and Solvent Structure

Dependence of equilibrium and rate constants on temperature and pressure

The volume of activation for benzyl chloride hydrolysis and its pressure dependence

Contact Info

Product

Resources

About