Diffusion Coefficients from Capillary Flow

Methods are presented for determining molecular diffusion coefficients by using data from capillary flow experiments. These methods are based on a numerical solution (presented in a previous paper) of the partial differential equation describing the combined mechanisms of flow and diffusion. Results from this numerical solution are given and compared with the approximate analytical solution of G. I. Taylor. The numerical solution is valid over a much larger time range. These methods are applied to experimental results for the fluid pairs water-potassium permanganate solution and amyl acetateorthoxylene. Both of these fluid pairs have approximately equal densities and viscosities. Graphical and numerical techniques are presented for deters mining diffusion coefficients from the flow data. Values obtained by these techniques are compared with values obtained by other methods. Introduction The molecular diffusion coefficient is known to be a variable in determining the amount of mixing in a miscible displacement process. The effect of molecular diffusion on dispersion in longitudinal flow through porous media has been examined by different investigators. These investigators concluded that at low velocities of flow, the amount of dispersion is approximately proportional to the molecular diffusion coefficient. The influence of diffusion on fingering, channeling, and overriding has been mentioned by other investigators. Recent studies have been made on the effects of molecular diffusion in connection with the problem of gravity segregation. Many different methods have been developed for the experimental determination of molecular diffusion coefficients. These methods differ mainly according to boundary conditions selected and analytical procedures used. Nevertheless, all of these methods have the condition in common that the bulk fluids in which diffusion is occurring are stationary with respect to each other. In connection with a series of papers on mixing in capillary flow, Taylor suggested the use of a flow method for determining molecular diffusion coefficients. Additional studies have been conducted on miscible displacements in capillary tubes, but the data from these studies were not used for the specific purpose of determining diffusion coefficients. The flow method proposed by Taylor results in a single value of the diffusion coefficient for the fluid pair used in the displacement experiments. This single value represents the true value for the fluid pair when the diffusion coefficient is independent of concentration. If the diffusion coefficient is a function of concentration, the single value obtained by the flow method gives an average value for the coefficient of the fluid pair. These average values are based on diffusion taking place over the entire range of concentration, i.e., from 0 per cent of one fluid to 100 per cent of that same fluid. In field applications of the miscible displacement process, gradients occur over the same range of concentration as are found in the displacements in capillary tubes. Molecular diffusion coefficients obtained from the capillary flow method should, therefore, be especially relevant to field operations. This investigation was undertaken to evaluate the feasibility of obtaining molecular diffusion coefficients from capillary flow experiments. In making this evaluation, diffusion coefficients were first determined for two systems from data obtained in capillary flow experiments. These values of the diffusion coefficient were then compared to values obtained by other methods. MIXING IN CAPILLARY FLOW-THEORETICAL The theoretical basis for determining molecular diffusion coefficients from capillary flow experiments is the partial differential equation relating the mechanisms of flow and diffusion. SPEJ P. 256^