Synopses & Reviews
Synopsis
Excerpt from Ion Activity in Homogeneous Catalysis; The Velocity of Hydrolysis of Ethyl Acetate
As a result of considerable evidence, Mac Innes (Jour. Amer. Chem. Soc. 41, 1086 1919]) has arrived at the conclusion that in solutions of the same molality of hydrochloric acid, lithium, sodium, and potassium chlorides, the chlorine ion has the same activity. He further made the assumption that in a solution of a given strength, the activities of the potassium and chlorine ions are the same. These hypotheses received considerable confirmation in dilute solutions from the electromotive force measurements of Ming Chow (Jour. Amer. Chem. Soc. 42, 477 1920]) and in concentrated solutions by Harned (Jour. Amer. Chem. Soc. 42, 1808 1920]). On the basis of these assumptions, Harned calculated from existing electromotive force data the individual ion activity coefficients of these uni-univalent electrolytes. If Mac Innes' assumptions are correct it follows from these calculations that the activity coefficient of the hydrogen ion in dilute solutions of hydrochloric acid decreases until a concentration of 0.15 M. is reached and then increases quite rapidly. In any event, this activity coefficient must exhibit a minimum in the neighborhood of from 0.1 M. to 0.2 M. concentration.
These conclusions, if true, or valid within narrow limits, will be of considerable importance in the calculation of equilibria in solutions as well as homogeneous catalysis. Consequently, this investigation was undertaken with the purpose of finding out whether further support for the above hypothesis could be obtained from a study of hydrogen ion catalysis.
It has been found that the monomolecular velocity constant of hydrolysis of ethyl acetate in dilute solutions of hydrochloric acid is roughly proportional to the concentration of the acid. It was first thought that the velocity of hydrolysis was proportional to the hydrogen ion concentration, but it was soon found that the velocity constant increased with increasing acid concentration more rapidly than the hydrogen ion concentrations as computed from the conductance or conductance viscosity ratios.
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Synopsis
Excerpt from Ion Activity in Homogeneous Catalysis; The Velocity of Hydrolysis of Ethyl Acetate
Constant boiling hydrochloric acid was diluted to 3m, and checked by gravimetric analysis. All solutions of the acid were made from this sample by the weight method and were correct to within of the total hydrochloric acid content. Conductivity water freed from carbon dioxide by boiling was employed.
The sodium hydroxide and barium hydroxide solutions used to titrate the total acid (hydrochloric, and acetic formed during the hydrolysis of the ester) were kept in carbon dioxide free bottles. The sodium hydroxide solutions were freed from carbonate by the addition of small quantities of barium hydroxide.
About the Publisher
Forgotten Books publishes hundreds of thousands of rare and classic books. Find more at www.forgottenbooks.com
This book is a reproduction of an important historical work. Forgotten Books uses state-of-the-art technology to digitally reconstruct the work, preserving the original format whilst repairing imperfections present in the aged copy. In rare cases, an imperfection in the original, such as a blemish or missing page, may be replicated in our edition. We do, however, repair the vast majority of imperfections successfully; any imperfections that remain are intentionally left to preserve the state of such historical works.