Organic transfer, simple experiments

Simple Experiments on Sea-to-Air Organic Transfer. Both jet and film drops, mixed upward into the atmosphere by turbulence, account... 

As might be expected, the results from both theory and experiment suggest that the solution is more than a simple spectator, and can participate in the surface physicochemical processes in a number of important ways [Cao et al., 2005]. It is well established from physical organic chemistry that the presence of a protic or polar solvent can act to stabilize charged intermediates and transition states. Most C—H, O—H, C—O, and C—C bond breaking processes that occur at the vapor/metal interface are carried out homolytically, whereas, in the presence of aqueous media, the hetero-lytic pathways tend to become more prevalent. Aqueous systems also present the opportunity for rapid proton transfer through the solution phase, which opens up other options in terms of reaction and diffusion. 

Recently, we are also able to perform liquid-liquid extractions of water-soluble dyes from water to organic solvents like toluene using the unimolecular dendritic micelles as extractants. These guest-host properties of the modified poly(propylene imine) dendrimers make use of the basic nature of the interior of the dendrimer. Therefore, it is possible to transfer dyes like Bengal Rose into toluene. Although simple tri-octylamines are capable of transferring these dyes as well, it is evident from the experiments that unimolecular dendritic inverted micelles are much more selective, probably due to the shielding effect of the apolar shell [70]. 

Many laboratories, including our own, have used the Marcus equation empirically as a relatively simple and convenient framework for describing the differences in the intrinsic difficulty for related reactions, after correction for differences in the reaction thermodynamic driving force. This has led to the determination of the Marcus intrinsic barriers for a variety of proton transfer reactions by experiment and through calculations [58-65], This compilation of intrinsic reaction barriers represents an attempt to compress an essential feature of these kinetic barriers to a single experimental parameter. An examination of the substituent effects on these intrinsic barriers has provided useful insight into the transition state for organic reactions [66],... 

---