Role of solvation dynamics in the kinetics of solvolysis reactions in microreactors

Abstract

In this contribution we attempt to correlate the dynamical states of water molecules in reverse micelles with a solvolysis reaction in accordance with the activation energy barrier crossing model at the micellar interface. Precise measurement of the different dynamical states of water molecules at the reverse micellar interface with various degrees of hydration is achieved through temperature-dependent solvation dynamics of coumarin 523. The rotational anisotropy studies along with a wobbling-in-cone analysis show that the probe residing at the micellar interface pointing towards the core water experiences less microviscosity at elevated temperature. The consequences of the dynamical freedom of the water at elevated temperature in the solvolysis reaction of benzoyl chloride have also been explored. The accelerated rate of solvolysis has been correlated with the increased solvation dynamics, both of which are associated with a temperature-induced transition of bound to free type water molecules at the micellar interface.

Role of Solvation Dynamics in Excited State Proton Transfer of 1‐Naphthol in Nanoscopic Water Clusters Formed in a Hydrophobic Solvent

“…water–DX interface). The bound to free type transition of water molecules with temperature is assumed to be governed by an Arrhenius type of activation energy barrier crossing model (46,47). We fit an Arrhenius plot using the <τ s > values listed in Table 2 (Fig.…”

Solvent dynamics in a reverse micellar water-pool: a spectroscopic investigation of DDAB–cyclohexane–water systems

“…Such temperature induced transition could be correlated with an Arrhenius type of transition in the following manner. It has been established in earlier studies 31,32,66,67,75,76 that the transition of water molecules at the RM and other microheterogeneous assemblies follows an Arrhenius type barrier crossing model given as:…”

Interfacial water with special electron donor properties: Effect of water–surfactant interaction in confined reversed micellar environments and its influence on the coordination chemistry of a copper complex

“…They have shown that water molecules when restricted to the nanometer-scale core of the aggregates behave differently from the bulk as a result of the specific interactions and confined geometries. In this way, recently Verma et al [60] have correlated the dynamical states of water molecules in reverse micelles with the solvolysis reaction of benzoyl chloride in AOT/ isooctane RMs at different W 0 values and temperatures. The observed acceleration of the solvation dynamics with the water content and the temperature increase supports the general view that the mobility of the water molecules in RM increases due to the transition of surface-bound water to free water.…”