Plate height diffusion

In these expressions, dp is the particle diameter of the stationary phase that constitutes one plate height. D is the diffusion coefficient of the solute in the mobile phase. 

The reduced velocity compares the mobile phase velocity with the velocity of the solute diffusion through the pores of the particle. In fact, the mobile phase velocity is measured in units of the intraparticle diffusion velocity. As the reduced velocity is a ratio of velocities then, like the reduced plate height, it also is dimensionless. Employing the reduced parameters, the equation of Knox takes the following form... 

The curves represent a plot of log (h ) (reduced plate height) against log (v) (reduced velocity) for two very different columns. The lower the curve, the better the column is packed (the lower the minimum reduced plate height). At low velocities, the (B) term (longitudinal diffusion) dominates, and at high velocities the (C) term (resistance to mass transfer in the stationary phase) dominates, as in the Van Deemter equation. The best column efficiency is achieved when the minimum is about 2 particle diameters and thus, log (h ) is about 0.35. The optimum reduced velocity is in the range of 3 to 5 cm/sec., that is log (v) takes values between 0.3 and 0.5. The Knox... 

The contribution to the plate height from molecular diffusion in the mobile phase arises from the natural tendency of the solute band to diffuse away from the zone center as it moves through the column [59,60,63,64]. Its value is proportional to the diffusion coefficient and the. time the sample spends in the column. Its contribution to the total plate height is given by... 

The A term represents the contribution from eddy diffusion, the B term the contribution from longitudinal diffusion, and the C terms the contributions from mass transfer in the mobile and stationary phases to the total column plate height. By differentiating equation (1.31) with respect to the mobile phase velocity and setting the result equal to zero, the optimum values of mobile phase velocity (u ) and plate height (HETP ) can be obtained. 

In liquid chronatography where diffusion coefficients are saall, the contribution of to the plate height is ften negligible. Diffusion coefficients are much larger in gases and hence is More inportant, particularly at low Mobile phase velocities. 

The diffusivities thus obtained are necessarily effective diffusivities since (1) they reflect a migration contribution that is not always negligible and (2) they contain the effect of variable properties in the diffusion layer that are neglected in the well-known solutions to constant-property equations. It has been shown, however, that the limiting current at a rotating disk in the laminar range is still proportional to the square root of the rotation rate if the variation of physical properties in the diffusion layer is accounted for (D3e, H8). Similar invariant relationships hold for the laminar diffusion layer at a flat plate in forced convection (D4), in which case the mass-transfer rate is proportional to the square root of velocity, and in free convection at a vertical plate (Dl), where it is proportional to the three-fourths power of plate height. 

The Poppe plot is a log-log plot of H/uq = t(JN versus the number of plates with different particle sizes and with lines drawn at constant void time, t(). H is the plate height, Vis the number of plates, and u() is the fluid velocity (assumed equal to the void velocity). The quantity H/u() is called the plate time, which is the time for a theoretical plate to develop and is indicative of the speed of the separation, with units of seconds. In the Poppe plot, a number of parameters including the maximum allowable pressure drop, particle diameter, viscosity, flow resistance, and diffusion coefficient are held constant. 

FIGURE 6.1 A Poppe plot for the required plate number in conventional HPLC. The parameters are taken from Poppe s original paper (Poppe, 1997). The parameters are maximum pressure AP = 4x 107 Pa, viscosity / = 0.001 Pa/s, flow resistance factor

diffusion coefficient D= lx 1CT9 m2/s, and reduced plate height parameters using Knox s plate height model are A — 1, B— 1.5, C = 0.05. 

Diffusion rates in liquids (LC) are typically three to four orders of magnitude less than in gases (GC). The lower mobile-phase diffusivity Dm affects two of the plate-height terms in liquid chromatography given in Table 19.1. First, the B/u term is small. Secondly, the Cmu term is large. The Csu term is small in many LC applications where the stationary phase is only a monolayer of liquid bonded to the surface of a solid... 

H is the plate height (cm) u is linear velocity (cm/s) dp is particle diameter, and >ni is the diffusion coefficient of analyte (cm /s). By combining the relationships between retention time, U, and retention factor, k tt = to(l + k), the definition of dead time, to, to = L u where L is the length of the column, and H = LIN where N is chromatographic efficiency with Equations 9.2 and 9.3, a relationship (Equation 9.4) for retention time, tt, in terms of diffusion coefficient, efficiency, particle size, and reduced variables (h and v) and retention factor results. Equation 9.4 illustrates that mobile phases with large diffusion coefficients are preferred if short retention times are desired. 

Equation 5 Knox equation, with reduced plate height, h reduced velocity (m dpID ), V, coefficient B, describing axial diffusion (typical value 2) coefficient A, describing bed homogeneity (typical value 1-2) and coefficient C, describing mass transfer (typical value 0.05). 

In order to compare data obtained with otherwise similar chromatographic systems in which only the particle size of the column packing and solute diffusivity may vary, Eq. (21) should be written in dimensionless form. Using an approach taken from chemical engineering, Knox (7, 34) has shown that a corresponding reduced plate height equation is given by Eq. (22)... 

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