The statistical method of least squares has been applied to the estimation of energy and entropy of activation when there is available a variable number of experimental values of the kinetic constant, at several temperatures.Furthermore, the method is described, by which the variances of the estimates can be calculated, and significance tests applied to them.
Hybridation et rCaetivitC 11. -Hydrolysc-, par l'eau, dcs bromurcs dc? proyyle normal, d'allylc e 1 proyaryyle P. J. C. FIERENS (*) et P. KRUYS (Bruxelles) SUMMARY Arrhenius parameters are determined for the hydrolysis of n-propyl-, allyl-and propargyl bromides, in water and in the mixture: water (59,lx)dioxane (40,9 yo). CII,3-CH2-CH,-Br water : E : 24,4 log PZ : 11,4 water-dioxane : E : 21,48 log PZ : 8,75 CH,= CH-CH,-Br water : E : 22,61 log PZ : 11,80 water-dioxane : E : 19,35 log PZ : 8,7G CH=C-CH2-Br water : E : 25,O log P Z : 11,54 water-dioxane : E : 20,7 log PZ : 8,21
SUMMARYThe influence of carbon -carbon triple, double and single bond on the reactivity of an adjacent carbon is interpreted on the basis of two competitive factors: inductive (related to the hybridization type) and mesomeric effects.A general analysis is applied to kinetic data pertaining to nucleophilic substitution reactions of varied mechanism.
The kinetic study of the alcaline hydrolysis of methyl acrylate and propiolate, in acetone 70% — water 30%, have been made.
The rate of hydrolysis of methyl propiolate is to fast to be measured: at‐12° the reaction is finished in less than 4 minutes.
In the case of methyl acrylate the Arrhenius parameters are: E=12,9 Kcal./mole log PZ=8,27.
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