Back-diffusion

Commercially available membranes are usually reinforced with woven, synthetic fabrics to improve the mechanical properties. Several hundred thousand square meters of IX membranes are now produced aimuaHy, and the mechanical and electrochemical properties are varied by the manufacturers to suit the proposed appHcations. The electrochemical properties of most importance for ED are (/) the electrical resistance per unit area of membrane (2) the ion transport number, related to current efficiency (2) the electrical water transport, related to process efficiency and (4) the back-diffusion, also related to process efficiency. 

Back-diffusion is the transport of co-ions, and an equivalent number of counterions, under the influence of the concentration gradients developed between enriched and depleted compartments during ED. Such back-diffusion counteracts the electrical transport of ions and hence causes a decrease in process efficiency. Back-diffusion depends on the concentration difference across the membrane and the selectivity of the membrane the greater the concentration difference and the lower the selectivity, the greater the back-diffusion. Designers of ED apparatus, therefore, try to minimize concentration differences across membranes and utilize highly selective membranes. Back-diffusion between sodium chloride solutions of zero and one normal is generally [Pg.173]

The system can be made more sophisticated through the addition of fused silica restrictors acting as bleeds, thus preventing back diffusion of analytes towards the solenoid valves. Additional pre-concentration stages can also be provided between the primary and secondary columns to reduce the peak widths introduced to the secondary column. 

Its main features are given by the use of a stream of inert carrier gas which percolates through a bed of an adsorbent covered with adsorbate and heated in a defined way. The desorbed gas is carried off to a detector under conditions of no appreciable back-diffusion. This means that the actual concentration of the desorbed species in the bed is reproduced in the detector after a time lag which depends on the flow velocity and the distance. The theory of this method has been developed for a linear heating schedule, first-order desorption kinetics, no adsorbable component in the entering carrier gas (Pa = 0), and the Langmuir concept, and has already been reviewed (48, 49) so that it will not be dealt with here. An analysis of how closely the actual experimental conditions meet the idealized model is not available. 

This result was taken as an experimental eonfirmation of the model developed by Sehmiekler [7]. However, it appeared somehow eontradictory with other results obtained with SECM. It was also suggested that eoneentration polarization phenomena occurring at the aqueous side are negligible as the whole potential drop is presumably developed in the benzene phase. This assumption can be qualitatively verified by evaluating a simplified expression for the potential distribution based on a back-to-back diffuse double layer [40,113],... 

Residual current in polarography. In the pragmatic treatment of the theory of electrolysis (Section 3.1) we have explained the occurrence of a residual current on the basis of back-diffusion of the electrolysis product obtained. In conventional polarography the wave shows clearly the phenomenon of a residual current by a slow rise of the curve before the decomposition potential as well as beyond the potential where the limiting current has been reached. In order to establish the value one generally corrects the total current measured for the current of the blank solution in the manner illustrated in Fig. 3.16 (vertical distance between the two parallel lines CD and AB). However, this is an unreliable procedure especially in polarography because, apart from the troublesome saw-tooth character of the i versus E curve, the residual current exists not only with a faradaic part, which is caused by reduction (or oxidation)... 

The diaphragm cell consists of multiple electrolytic cells having the anode plates and cathodes mounted vertically and parallel to each other. The cathodes, often flat hollow perforated steel structures that are covered with asbestos fibers, serve as the diaphragm that prevents the mixing of hydrogen and chlorine and back diffusion of hydroxide (OH) ions from the cathode to the anode. Brine fed into the cell is decomposed to approximately half of its original concentration to produce chlorine gas at the anode and hydrogen and sodium hydroxide at the cathode. 

Since operation in an autothermal mode implies a feedback of energy to preheat the feed, provision must be made for ignition of the reactor in order to attain steady-state operation. The ordinary gas burner and many other rapid combustion reactions are examples of autothermal reactions in which the reactants are preheated to the reaction temperature by thermal conduction and radiation. (Back diffusion of free radicals also plays an important role in many combustion processes.)... 

The experiments should preferably be performed under sink conditions (e.g., the drug concentration on the receiver side should be less than 10% of the concentration on the donor side during an experiment) in order to avoid bias by back-diffusion of significant amount of compound from the receiver chamber and to... 

The obvious technological advantage of a heterogeneous catalyst is that it can be easily separated from reactants and products. However, the serious physical problem is diffusion of reactants to active centers on the surface of the catalyst and back diffusion of the formed intermediate and final products from the surface into the solution. This duffusion occurs much more slowly in the liquid phase compared to the gas phase. The problem of effectiveness of the heterogeneous catalyst in comparison with the homogeneous catalyst is closely connected with the problem of diffusion and sorption on the surface in the liquid phase. 

Dioxygen and oxidized substances react on the surface of the catalyst only. The pure heterogeneous reaction occurs only after diffusion of reactants to the catalytic surface and back diffusion of products from the surface into the solution. A combination of a few mechanisms of such types are possible. 

Various works has pointed out the role of the nanostructure of the catalysts in their design.18-26 There is a general agreement that the nanostructure of the oxide particles is a key to control the reactivity and selectivity. Several papers have discussed the features and properties of nanostructured catalysts and oxides,27-41 but often the concept of nanostructure is not clearly defined. A heterogeneous catalyst should be optimized on a multiscale level, e.g. from the molecular level to the nano, micro- and meso-scale level.42 Therefore, not only the active site itself (molecular level) is relevant, but also the environment around the active site which orients or assist the coordination of the reactants, may induce sterical constrains on the transition state, and affect the short-range transport effects (nano-scale level).42 The catalytic surface process is in series with the transport of the reactants and the back-diffusion of the products which should be concerted with the catalytic transformation. Heat... 

Rogers, H.R. 1997, Influence of suspended sohds and back diffusion on organic contaminant uptake by semi-permeable membranes (SPMDs). Chemosphere 35 1651—1658. 

The EOD coefficient, is the ratio of the water flux through the membrane to the proton flux in the absence of a water concentration gradient. As r/d,3g increases with increasing current density during PEMFC operation, the level of dehydration increases at the anode and normally exceeds the ability of the PEM to use back diffusion to the anode to achieve balanced water content in the membrane. In addition, accumulation of water at the cathode leads to flooding and concomitant mass transport losses in the PEMFC due to the reduced diffusion rate of O2 reaching the cathode. 

Thin membranes have the advantage of low area specific conductivities and more favorable back diffusion of water in comparison with thicker membranes. In the former case, this means that membranes with lower conductivity values could be tolerated. Analysis of voltage loss versus membrane thickness and specific conductivity has revealed that, if a membrane voltage loss of 25 mV at a current density 1 A cm can be tolerated, then existing materials with conductivity values similar to Nation (0.1 S cm i) could be prepared as 20-30 pm thick membranes. However, thinner membranes also typically exhibit lower mechanical strength than their thicker counterparts and can therefore fail earlier. Therefore, future materials might be suitable with just half the specific conductivity if they can be prepared into membranes of half the thickness and still possess sufficient mechanical strength. ... 

After testing a number of DLs with and without MPLs, Lin and Nguyen [108] postulated that the MPL seemed to push more liquid water back to the anode through the membrane. Basically, the small hydrophobic pores in the MPL result in low liquid water permeability and reduce the water transport from the CL toward the DL. Therefore, more liquid water accumulated in the CL is forced toward the anode (back diffusion). This reduces the amount of water removed through the cathode DL, decreases the number of blocked pores within the cathode diffusion layer, and improves the overall gas transport from the DL toward the active zones. 

To reduce methanol crossover and improve water back diffusion through the membrane in passive DMFCs, Kim et al. [179] designed an MEA with... 

Peled ef al. [177] also designed a novel MEA in order to improve the water back diffusion from fhe cathode to the anode side. They used a liquid-water barrier layer (LWBL), which consisted of a paste, made out of PTFE and carbon black particles, fhat was inserted in the pores of fhe CFP to form a layer inside fhe paper. Up to seven layers were necessary in order to achieve a uniform layer of 20-50 pm in thickness. Testing showed that the LWBL on the cathode DL creates a hydraulic pressure that forces (or pushes) the water back from fhe cafhode toward the anode, thus improving the cell s water management at different operating conditions. 

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