Coalescence, Partial Coalescence, and Noncoalescence of an Aqueous Drop at an Oil-Water Interface under an Electric Field.

Drop-interface interaction under an electric field is relevant in commercial desalters wherein water droplets suspended in oil coalesce under an electric field, move down under gravity, and eventually coalesce with the water pool at the bottom of the desalter. In this work, we report our observation that the transition from coalescence to partial coalescence can be described by a critical electrocapillary number and is independent of the Ohnesorge number. On the other hand, the partial coalescence to noncoalescence transition depends upon both the electrocapillary number and the Ohnesorge number. The bridge during partial coalescence exhibits an electrocapillary-number-independent growth and collapse dynamics, although the transition time for growth to collapse depends upon the electrocapillary number (CaE). Lastly, contrary to previous studies, our results indicate that the secondary droplet size varies as CaE3/2 unlike the CaE1/2 reported in the literature.

Remarkable decrease in the viscosity of waxy crude oil under an electric field.

Uninterrupted transport of waxy crude oil through pipelines remains a pressing concern for the petroleum industry. When the ambient temperature falls below the pour point of the crude, deposition of wax particles may lead to complete blockage of the pipeline. We demonstrate that the application of a DC electric field to waxy crude below its pour point can effectively break the wax network and also reduce the viscosity by up to two orders of magnitude. We have studied the dynamics of the change in viscosity during and after application of an electric field. Three regimes are observed. First is the induction regime, where viscous stresses dominate and the viscosity remains unchanged. During the intermediate and final regimes, the decrease in viscosity follows first order kinetics with rate constants proportional to the strength of the electric field and to the square of the strength, respectively. Microscopic evidence shows that some network connections break during the intermediate regime, whereas in the final regime, further fragmentation of the pieces of the broken network occurs. This is accompanied by aggregation of fine wax fragments. After cessation of the field, the viscosity increases gradually. The rate and the extent of recovery of viscosity depend only on the value of viscosity at the point of cessation of the field. That the breakage of the network occurs, even in the absence of shear, has been demonstrated. Through measurement of the dielectric constants and conductivities of the crude oil and its component phases, we have shown that the wax network experiences compressive Maxwell stress, which is dominated by the electric field within the wax particles.

Elucidation of band structure of charge storage in conducting polymers using a redox reaction.

A novel technique to investigate charge storage characteristics of intrinsically conducting polymer films has been developed. A redox reaction is conducted on a polymer film on a rotating disk electrode under potentiostatic condition so that the rate of charging of the film equals the rate of removal of the charge by the reaction. The voltammogram obtained from the experiment on polyaniline film using Fe(2+)/Fe(3+) in HCl as the redox system shows five distinct linear segments (bands) with discontinuity in the slope at specific transition potentials. These bands are the same as those indicated by electron spin resonance (ESR)/Raman spectroscopy with comparable transition potentials. From the dependence of the slopes of the bands on concentration of ferrous and ferric ions, it was possible to estimate the energies of the charge carriers in different bands. The film behaves as a redox capacitor and does not offer resistance to charge transfer and electronic conduction.

Forecasting the Problem of Excessive Oil Entrainment in a Desalter Using Spinning Drop Method.

Frequent desalter upsets in the refineries processing opportunity crude oils are often triggered by a rapid and uncontrollable buildup of the rag layer, a thick water-in-oil emulsion, at the oil-brine interface. This is caused by spontaneous emulsification of brine in oil. This study investigates a unique observation from a spinning drop (SD) tensiometer, revealing the low apparent interfacial tension and rigidity of SD caused by spontaneous emulsification. Fine droplets of brine generated through spontaneous emulsification decorate the SD surface and form a stable, low-energy bilayer. Simulated rag layers using the brines from upset incidences exhibit similar behavior, indicating that spontaneous emulsification is driven by chemical species in brine, which promote osmotic water transport. The rate of rag layer buildup correlates with the rate of spontaneous emulsification, with the temperature coefficient of interfacial tension reduction serving as a sensitive indicator. An imminent upset in the operation can be forecasted by measuring this temperature coefficient, enabling preventive measures.

Data on primary hydration characteristics of aqueous electrolytes.

The data presented in this article support the research article entitled "Development of a rationale for decoupling osmotic coefficient of electrolytes into electrostatic and nonelectrostatic contributions" (Sahu and Juvekar, 2018) [1]. In this article, we have presented the plots of osmotic coefficients against molality for more than hundred aqueous single electrolytes at 25 °C. The linear regions in these plots are marked to show that they are present in all these electrolytes and that these regions extend over a wide range of concentrations. Slopes of the linear regions are used to estimate the primary molar hydration volume as well as the primary hydration number of these electrolytes. These values are also listed and the method of estimation is presented with sample calculation. These data, not only reinforce the observations made in the main article but also provide useful measures for estimation of the nonelectrostatic contribution to the osmotic coefficient.

Flexible ring polymers in an obstacle environment: Molecular theory of linear viscoelasticity.

We formulate a coarse-grained mean-field approach to study the dynamics of the flexible ring polymer in any given obstacle (gel or melt) environment. The similarity of the static structure of the ring polymer with that of the ideal randomly branched polymer is exploited in formulating the dynamical model using aspects of the pom-pom model for branched polymers. The topological constraints are handled via the tube model framework. Based on our formulation we obtain expressions for diffusion coefficient D, relaxation times tau, and dynamic structure factor g(k,t). Further, based on the framework we develop a molecular theory of linear viscoelasticity for ring polymers in a given obstacle environment and derive the expression for the relaxation modulus G(t). The predictions of the theoretical model are in agreement with previously proposed scaling arguments and in qualitative agreement with the available experimental results for the melt of rings.