Factors influencing mass transport rate

In FPTRMS, transport of the reactive species of interest from the reactor to the detector can make a contribution to the observed time dependence such that the chemical kinetics becomes convoluted with mass transport rates. This will have to be accounted for in data analysis if reliable rate coefficients are to be obtained. If the physical rate processes are sufficiently fast they will make a negligible contribution to the kinetics. In this section we examine the above four factors to see when they influence the chemical kinetics. The first, third, and fourth items put an upper limit on the rate at which decays and growths can be reliably determined, and the second one sets a lower limit on the decay rate. 

To understand the danger in proposing which reactions takes place to provide the required ES current on the basis of the standard electrode potentials alone, one must consider that several other factors influence the actual rate of a specific reaction. Assuming that mass transport is not the limiting factor, other processes such as the electron transfer rate at the electrode surface, chemical reactions preceding the electron transfer, or chemical... 

Influence of the Kinetics of Electron Transfer on the Faradaic Current The rate of mass transport is one factor influencing the current in a voltammetric experiment. The ease with which electrons are transferred between the electrode and the reactants and products in solution also affects the current. When electron transfer kinetics are fast, the redox reaction is at equilibrium, and the concentrations of reactants and products at the electrode are those specified by the Nernst equation. Such systems are considered electrochemically reversible. In other systems, when electron transfer kinetics are sufficiently slow, the concentration of reactants and products at the electrode surface, and thus the current, differ from that predicted by the Nernst equation. In this case the system is electrochemically irreversible. 

Scale-Up Principles. Key factors affecting scale-up of reactor performance are nature of reaction zones, specific reaction rates, and mass- and heat-transport rates to and from reaction sites. Where considerable uncertainties exist or large quantities of products are needed for market evaluations, intermediate-sized demonstration units between pilot and industrial plants are usehil. Matching overall fluid flow characteristics within the reactor might determine the operative criteria. Ideally, the smaller reactor acts as a volume segment of the larger one. Elow distributions are not markedly influenced by... 

The result is shown in Figure 10, which is a plot of the dimensionless effectiveness factor as a function of the dimensionless Thiele modulus ( ), which is R.(k/Dwhere R is the radius of the catalyst particle and k is the reaction rate constant. The effectiveness factor is defined as the ratio of the rate of the reaction divided by the rate that would be observed in the absence of a mass transport influence. The effectiveness factor would be unity if the catalyst were nonporous. Therefore, the reaction rate is... 

Figure 10 shows that Tj is a unique function of the Thiele modulus. When the modulus ( ) is small (- SdSl), the effectiveness factor is unity, which means that there is no effect of mass transport on the rate of the catalytic reaction. When ( ) is greater than about 1, the effectiveness factor is less than unity and the reaction rate is influenced by mass transport in the pores. When the modulus is large (- 10), the effectiveness factor is inversely proportional to the modulus, and the reaction rate (eq. 19) is proportional to k ( ), which, from the definition of ( ), implies that the rate and the observed reaction rate constant are proportional to (1 /R)(f9This result shows that both the rate constant, ie, a measure of the intrinsic activity of the catalyst, and the effective diffusion coefficient, ie, a measure of the resistance to transport of the reactant offered by the pore stmcture, influence the rate. It is not appropriate to say that the reaction is diffusion controlled it depends on both the diffusion and the chemical kinetics. In contrast, as shown by equation 3, a reaction in solution can be diffusion controlled, depending on D but not on k. 

The mass transport influence is easy to diagnose experimentally. One measures the rate at various values of the Thiele modulus the modulus is easily changed by variation of R, the particle size. Cmshing and sieving the particles provide catalyst samples for the experiments. If the rate is independent of the particle size, the effectiveness factor is unity for all of them. If the rate is inversely proportional to particle size, the effectiveness factor is less than unity and

experimental points allow triangulation on the curve of Figure 10 and estimation of Tj and ( ). It is also possible to estimate the effective diffusion coefficient and thereby to estimate Tj and ( ) from a single measurement of the rate (48). 

Rates and selectivities of soHd catalyzed reactions can also be influenced by mass transport resistance in the external fluid phase. Most reactions are not influenced by external-phase transport, but the rates of some very fast reactions, eg, ammonia oxidation, are deterrnined solely by the resistance to this transport. As the resistance to mass transport within the catalyst pores is larger than that in the external fluid phase, the effectiveness factor of a porous catalyst is expected to be less than unity whenever the external-phase mass transport resistance is significant, A practical catalyst that is used under such circumstances is the ammonia oxidation catalyst. It is a nonporous metal and consists of layers of wire woven into a mesh. 

Much LC-MS work is carried out in a qualitative or semi-quantitative mode. Development of quantitative LC-MS procedures for polymer/additive analysis is gaining attention. When accurate quantitation is necessary, it is important to understand in depth the experimental factors which influence the quantitative response of the entire LC-MS system. These factors, which include solvent composition, solvent flow-rate, and the presence of co-eluting species, exert a major influence on analyte mass transport and ionisation efficiency. Analyte responses in MS procedures can be significantly affected by the nature of the organic modifier used in the RPLC... 

Diffusion of small molecular penetrants in polymers often assumes Fickian characteristics at temperatures above Tg of the system. As such, classical diffusion theory is sufficient for describing the mass transport, and a mutual diffusion coefficient can be determined unambiguously by sorption and permeation methods. For a penetrant molecule of a size comparable to that of the monomeric unit of a polymer, diffusion requires cooperative movement of several monomeric units. The mobility of the polymer chains thus controls the rate of diffusion, and factors affecting the chain mobility will also influence the diffusion coefficient. The key factors here are temperature and concentration. Increasing temperature enhances the Brownian motion of the polymer segments the effect is to weaken the interaction between chains and thus increase the interchain distance. A similar effect can be expected upon the addition of a small molecular penetrant. 

As can be concluded from this short description of the factors influencing the overall reaction rate in liquid-solid or gas-solid reactions, the structure of the stationary phase is of significant importance. In order to minimize the transport limitations, different types of supports were developed, which will be discussed in the next section. In addition, the amount of enzyme (operative ligand on the surface of solid phase) as well as its activity determine the reaction rate of an enzyme-catalyzed process. Thus, in the following sections we shall briefly describe different types of chromatographic supports, suited to provide both the high surface area required for high enzyme capacity and the lowest possible internal and external mass transfer resistances. 

The published values for the activation energies and pre-exponential factors of transesterification and glycolysis vary significantly. Catalysts and stabilizers influence the overall reaction rate markedly, and investigations using different additives cannot be compared directly. Most investigations are affected by mass transport and without knowledge of the respective mass transport parameters, kinetic results cannot be transferred to other systems. 

For gas-solid heterogeneous reactions particle size and average pore diameter will influence the reaction rate per unit mass of solid when internal diffusion is a significant factor in determining the rate. The actual mode of transport within the porous structure will depend largely on the pore diameter and the pressure within the reactor. Before developing equations which will enable us to predict reaction rates in porous solids, a brief consideration of transport in pores is pertinent. 

This expression of the current-potential relationship is totally general. For each particular situation, the expressions of the rate constants (through a given kinetic model) and of the limiting currents and mass transport coefficients should be provided to analyze the influence of the different factors that can control the global rate. 

C02 concentrations (Rau et al. 1992 Pancost et al. 1997). Under conditions of abundant C02, mass transport into cells is unlikely to limit the rate of photosynthesis, so the large isotopic fractionation of rubisco should dominate the overall fractionation. There are many other factors that can influence Ephotosynthesis... 

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