And mass transport

Catalyst design is in a primitive stage. There are hardly any examples of tme design of catalysts (42). However, development of improved catalysts has been guided successfully in instances when the central issues were the interplay of mass transport and reaction. An example is catalysts used for hydroprocessing of heavy fossil fuels. 

S. G. Mueller, R. Eckstein, D. Hofmann, L. Kadinski, P. Kaufmann, M. Koelbl, E. Schmitt. Modelling of the PVT-SiC bulk growth process taking into account global heat transfer, mass transport and heat of crystal-Uzation and results on its experimental verification. Mater Sci Eorum 0 51, 1998. 

If a diffusion potential occurs inside the membrane, the relation between mass transport and electrochemical potential gradient — as the driving force for the diffusion of ions — has to be examined in more detail. This can be done by three different approaches ... 

This chapter attempts to give an overview of electrode processes, together with discussion of electron transfer kinetics, mass transport, and the electrode-solution interface. 

For quasi-reversible systems the limiting current is controlled by both mass transport and charge transfer ... 

Overall, the RDE provides an efficient and reproducible mass transport and hence the analytical measurement can be made with high sensitivity and precision. Such well-defined behavior greatly simplifies the interpretation of the measurement. The convective nature of the electrode results also in very short response tunes. The detection limits can be lowered via periodic changes in the rotation speed and isolation of small mass transport-dependent currents from simultaneously flowing surface-controlled background currents. Sinusoidal or square-wave modulations of the rotation speed are particularly attractive for this task. The rotation-speed dependence of the limiting current (equation 4-5) can also be used for calculating the diffusion coefficient or the surface area. Further details on the RDE can be found in Adam s book (17). 

Thermodynamic, mass transport, and kinetic considerations, which are reviewed in Ch. 2. 

Whitaker, S, Transport Processes with Heterogeneous Reaction. In Concepts and Design of Chemical Reactors Whitaker, S Cassano, AE, eds. Gordon and Breach Newark, NJ 1986 1. Whitaker, S, Mass Transport and Reaction in Catalyst Pellets, Transport in Porous Media 2, 269, 1987. 

Fig. 2 shows a schematic diagram of a micro-channel of reformer section to be examined in this study. A multi-physics computer-aided numerical model framework integrating kinetics, mass transport, and flow dynamics in micro-channel reactors has been established. 

The above brief analysis underlines that the porous structure of the carbon substrate and the presence of an ionomer impose limitations on the application of porous and thin-layer RDEs to studies of the size effect. Unless measurements are carried out at very low currents, corrections for mass transport and ohmic limitations within the CL [Gloaguen et ah, 1998 Antoine et ah, 1998] must be performed, otherwise evaluation of kinetic parameters may be erroneous. This is relevant for the ORR, and even more so for the much faster HOR, especially if the measurements are performed at high overpotentials and with relatively thick CLs. Impurities, which are often present in technical carbons, must also be considered, given the high purity requirements in electrocatalytic measurements in aqueous electrolytes at room temperature and for samples with small surface area. 

Interpretation of pubhshed data is often comphcated by the fact that rather complex catalytic materials are utilized, namely, poly disperse nonuniform metal particles, highly porous supports, etc., where various secondary effects may influence or even submerge PSEs. These include mass transport and discrete particle distribution effects in porous layers, as confirmed by Gloaguen, Antoine, and co-workers [Gloaguen et al., 1994, 1998 Antoine et al., 1998], and diffusion-readsorption effects, as shown by Jusys and co-workers for the MOR and by Chen and Kucemak for the ORR [Jusys et al., 2003 Chen and Kucemak, 2004a, b]. Novel approaches to the design of ordered nanoparticle arrays where nanoparticle size and interparticle distances can be varied independently are expected to shed hght on PSEs in complex multistep multielectron processes such as the MOR and the ORR. 

The success of SECM methodologies in providing quantitative information on the kinetics of interfacial processes relies on the availability of accurate theoretical models for mass transport and coupled kinetics, to allow the analysis of experimental data. The geometry of SECM is not conducive to exact analytical solution and hence a number of semiana-lytical [40,41], and numerical [8,10,42 46], methods have been introduced for a variety of problems. 

For small K, i.e., K = 0.5 in Fig. 17, the response of the equilibrium to the depletion of species Red] in phase 1 is slow compared to diffusional mass transport, and consequently the current-time response and mass transport characteristics are close to those predicted for hindered diffusion with an inert interface. As K is increased, the interfacial process responds more rapidly to the electrochemical perturbation in phase 1. The transfer of the target species across the interface generates an enhanced flux to the UME, causing... 

F. Garda-Ochoa, A. Santos 1996, (Coke effect in mass transport and morphology of Pt-AfiCfi and Ni-Mo-AfiCfi catalysts), AIChEJ. 42, 524. 

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... 

Experimental methods which yield precise and accurate data are essential in studying diffusion-based systems of pharmaceutical interest. Typically the investigator identifies a mechanism and associated mass transport model to be studied and then constructs an experiment which is consistent with the hypothesis being tested. When mass transport models are explicitly involved, experimental conditions must be physically consistent with the initial and boundary conditions specified for the model. Model testing also involves recognition of the assumptions and constraints and their effect on experimental conditions. Experimental conditions in turn affect the maintenance of sink conditions, constant surface area for mass transport, and constant and known hydrodynamic conditions. 

MZ Southard, DW Green, VJ Stella, KJ Himmelstein. Dissolution of ionizable drugs into unbuffered solution A comprehensive model for mass transport and reaction in the rotating disk geometry. Pharm Res 9 58-69, 1992. 

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. 

It is very easy to see that Eqs. (48) and (49) have similar form and yet they represent mass transport and heat transport resistance, respectively. What is needed is a connection between the two transport resistances, and this is accomplished by combining the two equations to eliminate RHS. The resulting combined mass-heat transport limited rate moisture uptake (W mh) is given by... 

Therefore, criteria in the selection of an electrode reaction for mass-transfer studies are (1) sufficient difference between the standard electrode potential of the reaction that serves as a source or sink for mass transport and that of the succeeding reaction (e.g., hydrogen evolution following copper deposition in acidified solution), and (2) a sufficiently low surface overpotential and rate of increase of surface overpotential with current density, so that, as the current is increased, the potential will not reach the level required by the succeeding electrode process (e.g., H2 evolution) before the development of the limiting-current plateau is complete. 

Lla. Landau. U., LBL-2702 Ph.D. thesis. University of California, Berkeley, January 1976. Lib. Landau, U., and Tobias, C. W., Mass Transport and Current Distribution in Channel Type Electrolyzers in the Laminar and Turbulent Flow Regimes, Ext. Abstr., No. 266, Electrochemical Society Meeting, Washington D.C., May 1976, 663. 

Mass Transport and Leaching. Organic substances can be moved... 

---