Mass transfer time constants

Fig. 2.16 Mixing, mass transfer and oxygen consumption in a bubble column bioreactor (Oosterhuis, 1984). r, reaction time constant, rmt mass transfer time constant, rmix mixing time constant. r02 oxygen consumption rate, vs superficial gas velocity.

Because of the much higher mass transfer time constants in comparison to two-phase systems a pure kinetic control of the reactions is normally observed for reactions in micellar solutions and micro emulsions. Even for a collision-controlled fluorescence quenching... 

Parameters describing equilibrium (AH, Kao, and gA) have been fitted simultaneously with a mass transfer time constant for water k, appropriate to their experimental set-up, and activation energy Ec and pre-exponential factors kco or kuo describing forward reaction through a third- or second-order rate law ... 

Assuming a constant surface area, dissolution at a solution-solid interface (Case I) results in linear kinetics in which the rate of mass transfer is constant with time (equation 1). Analytical solutions to the diffusion equation result in parabolic rates of mass transfer (, 16) (equation 2). This result is obtained whether the boundary conditions are defined so diffusion occurs across a progressively thickening, leached layer within the silicate phase (Case II), or across a growing precipitate layer forming on the silicate surface (Case III). Another case of linear kinetics (equation 1) may occur when the rate of formation of a metastable product or leached layer at the fresh silicate surface becomes equal to the rate at which this layer is destroyed at the aqueous... 

Comparison of equations 3 and 10 shows the essential difference between the stationary states of closed and continuous, open systems. For the closed system, equilibrium is the time-invariant condition. The total of each independently variable constituent and the equilibrium constant (a function of temperature, pressure, and composition) for each independent reaction (ATab in the example) are required to define the equilibrium composition Ca- For the continuous, open system, the steady state is the time-invariant condition. The mass transfer rate constant, the inflow mole number of each independently variable constituent, and the rate constants (functions of temperature, pressure, and composition) for each independent reaction are requir to define the steady-state composition Ca- It is clear that open-system models of natural waters require more information than closed-system models to define time-invariant compositions. An equilibrium model can be expected to describe a natural water system well when fluxes are small, that is, when flow time scales are long and chemical reaction time scales are short. 

Conceptual models of percutaneous absorption which are rigidly adherent to general solutions of Pick s equation are not always applicable to in vivo conditions, primarily because such models may not always be physiologically relevant. Linear kinetic models describing percutaneous absorption in terms of mathematical compartments that have approximate physical or anatomical correlates have been proposed. In these models, the various relevant events, including cutaneous metabolism, considered to be important in the overall process of skin absorption are characterized by first-order rate constants. The rate constants associated with diffusional events in the skin are assumed to be proportional to mass transfer parameters. Constants associated with the systemic distribution and elimination processes are estimated from pharmacokinetic parameters derived from plasma concentration-time profiles obtained following intravenous administration of the penetrant. 

The rate of heat removal from the washcoat is proportional to the heat transfer coefficient and to the temperature difference between the gas and the washcoat, while the rate of heat generation is the product of the rate of mass transfer times the heat of reaction (-AH), as indicated by Eqs. (3) and (4) below, where kr is a first-order reaction rate constant. At the steady state the rates of heat generation and removal are equal. 

Scaling with Residence Time and Mass Transfer Performance Constant... 

For the phenomena presented in Table 2.1, efficiency can be related to characteristic times by writing a balance of the extensity concerned. For a chemical plug-flow reactor (with an apparent first-order reaction or with heat/mass transfer at constant exchange coefficient), the quantity of this extensity is linearly related to its variation with respect to the reference time, yielding ordinary differential equations such as... 

Practically all calculations arrive directly or indirectly at the definition and the use of dimensionless parameters to characterize (and normalise) the reactive heterogenous system (Tables II and III). The parameters include constants of mass transfer, of reactions and of dimensions they express a ratio of reaction time/mass transfer time ... 

Other Models for Mass Transfer. In contrast to the film theory, other approaches assume that transfer of material does not occur by steady-state diffusion. Rather there are large fluid motions which constantiy bring fresh masses of bulk material into direct contact with the interface. According to the penetration theory (33), diffusion proceeds from the interface into the particular element of fluid in contact with the interface. This is an unsteady state, transient process where the rate decreases with time. After a while, the element is replaced by a fresh one brought to the interface by the relative movements of gas and Uquid, and the process is repeated. In order to evaluate a constant average contact time T for the individual fluid elements is assumed (33). This leads to relations such as... 

The time constant R /D, and hence the diffusivity, may thus be found dkecdy from the uptake curve. However, it is important to confirm by experiment that the basic assumptions of the model are fulfilled, since intmsions of thermal effects or extraparticle resistance to mass transfer may easily occur, leading to erroneously low apparent diffusivity values. 

R is rate of reaction per unit area, a is interfacial area per unit volume, S is solubiHty of solute in continuous phase, D is diffusivity of solute, k is rate constant, kj is mass-transfer coefficient, is concentration of reactive species, and Z is stoichiometric coefficient. When Dk is considerably greater (10 times) than Ra = aS Dk. 

Effective Interfacial Mass-Transfer Area a In a packed tower of constant cross-sectional area S the differential change in solute flow per unit time is given by... 

Time constants. Where there is a capacity and a throughput, the measurement device will exhibit a time constant. For example, any temperature measurement device has a thermal capacity (mass times heat capacity) and a heat flow term (heat transfer coefficient and area). Both the temperature measurement device and its associated thermowell will exhibit behavior typical of time constants. 

In the case of a temperature probe, the capacity is a heat capacity C == me, where m is the mass and c the material heat capacity, and the resistance is a thermal resistance R = l/(hA), where h is the heat transfer coefficient and A is the sensor surface area. Thus the time constant of a temperature probe is T = mc/ hA). Note that the time constant depends not only on the probe, but also on the environment in which the probe is located. According to the same principle, the time constant, for example, of the flow cell of a gas analyzer is r = Vwhere V is the volume of the cell and the sample flow rate. 

This equation is that of a first-order reaction process, and thus the fraction of material electrolysed at any instant is independent of the initial concentration. It follows that if the limit of accuracy of the determination is set at C, = 0.001 C0, the time t required to achieve this result will be independent of the initial concentration. The constant k in the above equation can be shown to be equal to Am/ V, where A is the area of the pertinent electrode, V the volume of the solution and m the mass transfer coefficient of the electrolyte.20 It follows that to make t small A and m must be large, and V small, and this leads to the... 

As an example, it may be supposed that in phase 1 there is a constant finite resistance to mass transfer which can in effect be represented as a resistance in a laminar film, and in phase 2 the penetration model is applicable. Immediately after surface renewal has taken place, the mass transfer resistance in phase 2 will be negligible and therefore the whole of the concentration driving force will lie across the film in phase 1. The interface compositions will therefore correspond to the bulk value in phase 2 (the penetration phase). As the time of exposure increases, the resistance to mass transfer in phase 2 will progressively increase and an increasing proportion of the total driving force will lie across this phase. Thus the interface composition, initially determined by the bulk composition in phase 2 (the penetration phase) will progressively approach the bulk composition in phase 1 as the time of exposure increases. 

HARRIOTT 25 suggested that, as a result of the effects of interfaeial tension, the layers of fluid in the immediate vicinity of the interface would frequently be unaffected by the mixing process postulated in the penetration theory. There would then be a thin laminar layer unaffected by the mixing process and offering a constant resistance to mass transfer. The overall resistance may be calculated in a manner similar to that used in the previous section where the total resistance to transfer was made up of two components—a Him resistance in one phase and a penetration model resistance in the other. It is necessary in equation 10.132 to put the Henry s law constant equal to unity and the diffusivity Df in the film equal to that in the remainder of the fluid D. The driving force is then CAi — CAo in place of C Ao — JPCAo, and the mass transfer rate at time t is given for a film thickness L by ... 

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