Randomly mass transfer

The situation is very much poorer for stmctured rather than random packings, in that hardly any data on Hq and have been pubHshed. Based on a mechanistic model for mass transfer, a way to estimate HETP values for stmctured packings in distillation columns has been proposed (91), yet there is a clear need for more experimental data in this area. 

Ordinary diffusion involves molecular mixing caused by the random motion of molecules. It is much more pronounced in gases and Hquids than in soHds. The effects of diffusion in fluids are also greatly affected by convection or turbulence. These phenomena are involved in mass-transfer processes, and therefore in separation processes (see Mass transfer Separation systems synthesis). In chemical engineering, the term diffusional unit operations normally refers to the separation processes in which mass is transferred from one phase to another, often across a fluid interface, and in which diffusion is considered to be the rate-controlling mechanism. Thus, the standard unit operations such as distillation (qv), drying (qv), and the sorption processes, as well as the less conventional separation processes, are usually classified under this heading (see Absorption Adsorption Adsorption, gas separation Adsorption, liquid separation). 

Various mathematical concepts and techniques have been used to derive the functions that describe the different types of dispersion and to simplify further development of the rate theory two of these procedures will be discussed in some detail. The two processes are, firstly, the Random Walk Concept [1] which was introduced to the rate theory by Giddings [2] and, secondly, the mathematics of diffusion which is both critical in the study of dispersion due to longitudinal diffusion and that due to solute mass transfer between the two phases. The random walk model allows the relatively simple derivation of the variance contributions from two of the dispersion processes that occur in the column and, so, this model will be the first to be discussed. 

The dispersion of a solute band in a packed column was originally treated comprehensively by Van Deemter et al. [4] who postulated that there were four first-order effect, spreading processes that were responsible for peak dispersion. These the authors designated as multi-path dispersion, longitudinal diffusion, resistance to mass transfer in the mobile phase and resistance to mass transfer in the stationary phase. Van Deemter derived an expression for the variance contribution of each dispersion process to the overall variance per unit length of the column. Consequently, as the individual dispersion processes can be assumed to be random and non-interacting, the total variance per unit length of the column was obtained from a sum of the individual variance contributions. 

Equation (14), although derived from the approximate random walk theory, is rigorously correct and applies to heterogeneous surfaces containing wide variations in properties and to perfectly uniform surfaces. It can also be used as the starting point for the random walk treatment of diffusion controlled mass transfer similar to that which takes place in the stationary phase in GC and LC columns. 

The term mass transfer is used to denote the transference of a component in a mixture from a region where its concentration is high to a region where the concentration is lower. Mass transfer process can take place in a gas or vapour or in a liquid, and it can result from the random velocities of the molecules (molecular diffusion) or from the circulating or eddy currents present in a turbulent fluid (eddy diffusion). 

Equation 10.4, which describes the mass transfer rate arising solely from the random movement of molecules, is applicable to a stationary medium or a fluid in streamline flow. If circulating currents or eddies are present, then the molecular mechanism will be reinforced and the total mass transfer rate may be written as ... 

In the previous section, the molecular basis for the processes of momentum transfer, heat transfer and mass transfer has been discussed. It has been shown that, in a fluid in which there is a momentum gradient, a temperature gradient or a concentration gradient, the consequential momentum, heat and mass transfer processes arise as a result of the random motion of the molecules. For an ideal gas, the kinetic theory of gases is applicable and the physical properties p,/p, k/Cpp and D, which determine the transfer rates, are all seen to be proportional to the product of a molecular velocity and the mean free path of the molecules. 

Experiments have been carried out on the mass transfer of acetone between air and a laminar water jet. Assuming that desorption produces random surface renewal with a constant fractional rate of surface renewal, v, but an upper limit on surface age equal to the life of the jet, r, show that the surface age frequency distribution function, 4>(t), for this case is given by ... 

Danckwerts assumed a random surface renewal process in which the probability of surface renewal is independent of its age. If s is the fraction of the total surface renewed per unit time, obtain the age distribution function for the surface and show that the mean mass transfer rate Na over the whole surface is ... 

Mass transfer in packed columns is a continuous, differential, process, so the transfer unit method should be used to determine the column height, as used in absorption see Section 11.14.2. However, it often convenient to treat them as staged processes and use the HETS for the packing employed. For random packings the HETS will, typically, range from 0.5 to 1.5 m, depending on the type and size of packing used. 

Diffusion is the movement of mass due to a spatial gradient in chemical potential and as a result of the random thermal motion of molecules. While the thermodynamic basis for diffusion is best apprehended in terms of chemical potential, the theories describing the rate of diffusion are based instead on a simpler and more experimentally accessible variable, concentration. The most fundamental of these theories of diffusion are Fick s laws. Fick s first law of diffusion states that in the presence of a concentration gradient, the observed rate of mass transfer is proportional to the spatial gradient in concentration. In one dimension (x), the mathematical form of Fick s first law is... 

Berkowitz B, Emmanuel S, Scher H (2008) Non-Fickian transport and multiple rate mass transfer in porous media Water Resour Res 44, D01 10.1029/2007WR005906 Bijeljic B, Blunt MJ (2006) Pore-scale modeling and continuous time random walk analysis of dispersion in porous media. Water Resour Res 42, W01202, D01 10.1029/2005WR004578 Blunt MJ (2000) An empirical model for three-phase relative permeability. SPE Journal 5 435-445... 

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