Concentration gradient, thickness

Thermal thickness fluctuations in pseudoemulsion films mean that the amounts of adsorbed oil will vary with film thickness as a consequence of different rates of transport of oil molecules arising from differences in concentration gradient. Thinner parts of the film will therefore experience a transient lowering of air-water surface tension relative to adjacent thicker parts of the film. The resultant surface tension gradient will drive liquid away from the thinner parts of the film to the thicker parts of the film, which will increase the concentration gradient. Thickness fluctuations will therefore be amplified and will tend to destabilize the film. Amplification of such thickness fluctuations is opposed by both disjoining pressures, if dfl woCWd < 0, and capillarity. 

O, a large current is detected, which decays steadily with time. The change in potential from will initiate the very rapid reduction of all the oxidized species at the electrode surface and consequently of all the electroactive species diffrising to the surface. It is effectively an instruction to the electrode to instantaneously change the concentration of O at its surface from the bulk value to zero. The chemical change will lead to concentration gradients, which will decrease with time, ultimately to zero, as the diffrision-layer thickness increases. At time t = 0, on the other hand, dc-Jdx) r. will tend to infinity. The linearity of a plot of i versus r... 

Either the and the two e s diffuse outward through the film to meet the 0 at the outer surface, or the oxygen diffuses inwards (with two electron holes) to meet the at the inner surface. The concentration gradient of oxygen is simply the concentration in the gas, c, divided by the film thickness, x and the rate of growth of the film dx/dt is obviously proportional to the flux of atoms diffusing through the film. So, from Pick s Law (eqn. (18.1)) ... 

An additional advantage to neutron reflectivity is that high-vacuum conditions are not required. Thus, while studies on solid films can easily be pursued by several techniques, studies involving solvents or other volatile fluids are amenable only to reflectivity techniques. Neutrons penetrate deeply into a medium without substantial losses due to absorption. For example, a hydrocarbon film with a density of Ig cm havii a thickness of 2 mm attenuates the neutron beam by only 50%. Consequently, films several pm in thickness can be studied by neutron reflecdvity. Thus, one has the ability to probe concentration gradients at interfaces that are buried deep within a specimen while maintaining the high spatial resolution. Materials like quartz, sapphire, or aluminum are transparent to neutrons. Thus, concentration profiles at solid interfaces can be studied with neutrons, which simply is not possible with other techniques. 

Such effects principally cannot be observed in multi band detectors such as a UV diode array detector or a Fourier transform infrared (FTIR) detector because all wavelengths are measured under the same geometry. For all other types of detectors, in principle, it is not possible to totally remove these effects of the laminar flow. Experiments and theoretical calculations show (8) that these disturbances can only be diminished by lowering the concentration gradient per volume unit in the effluent, which means that larger column diameters are essential for multiple detection or that narrow-bore columns are unsuitable for detector combinations. Disregarding these limitations can lead to serious misinterpretations of GPC results of multiple detector measurements. Such effects are a justification for thick columns of 8-10 mm diameter. 

Our picture of the transport process in these thick oxide layers is that there is a uniform concentration gradient of defects (cation vacancies and positive holes) across the layer. But it is important to notice that the oxidation flux is exactly twice that to be expected if diffusion alone were responsible for the transport of cation vacancies. The reason for this is, of course, that the more mobile positive holes set up an electric field which assists the transport of the slower-moving cation vacancies. 

When a polymer sheet of thickness L is immersed in the gas at a constant pressure, the surface concentration increases instantaneously, to a steady value which is then spread by diffusion throughout the whole bulk of the polymer sheet to finally give a uniform concentration. During the sorption the concentration gradients in the polymer decrease as the time progresses reducing the sorption... 

In this approach, it is assumed that turbulence dies out at the interface and that a laminar layer exists in each of the two fluids. Outside the laminar layer, turbulent eddies supplement the action caused by the random movement of the molecules, and the resistance to transfer becomes progressively smaller. For equimolecular counterdiffusion the concentration gradient is therefore linear close to the interface, and gradually becomes less at greater distances as shown in Figure 10.5 by the full lines ABC and DEF. The basis of the theory is the assumption that the zones in which the resistance to transfer lies can be replaced by two hypothetical layers, one on each side of the interface, in which the transfer is entirely by molecular diffusion. The concentration gradient is therefore linear in each of these layers and zero outside. The broken lines AGC and DHF indicate the hypothetical concentration distributions, and the thicknesses of the two films arc L and L2. Equilibrium is assumed to exist at the interface and therefore the relative positions of the points C and D are determined by the equilibrium relation between the phases. In Figure 10.5, the scales are not necessarily the same on the two sides of the interface. 

As the concentration gradient further increases (regime C), the radius of curvafure of premixed wings l cur decreases. When if becomes comparable wifh, for example, the preheat zone thickness Sj, typically O (1mm), one or both of fhe premixed flame wings can be merged to the trailing diffusion flame by having a bibrachial or cotton-bud shaped structure. 

Diffnsion finxes develop as a result of these concentration gradients. The layer of electrolyte where the concentration changes occur and within which the substances are transported by diffnsion is called the diffusion layer. Its thickness, 5 (the diffusion path length), depends on cell design features and on the intensity of convechve... 

In electrochemical systems with flat electrodes, all fluxes within the diffusion layers are always linear (one-dimensional) and the concentration gradient grad Cj can be written as dCfldx. For electrodes of different shape (e.g., cylindrical), linearity will be retained when thickness 5 is markedly smaller than the radius of surface curvature. When the flux is linear, the flux density under steady-state conditions must be constant along the entire path (throughout the layer of thickness 8). In this the concentration gradient is also constant within the limits of the layer diffusion layer 5 and can be described in terms of finite differences as dcjidx = Ac /8, where for reactants, Acj = Cyj - c j (diffusion from the bulk of the solution toward the electrode s surface), and for reaction products, Acj = Cg j— Cyj (diffusion in the opposite direction). Thus, the equation for the diffusion flux becomes... 

It follows that convection of the hqnid has a twofold influence It levels the concentrations in the bnlk liquid, and it influences the diffusional transport by governing the diffusion-layer thickness. Shght convection is sufficient for the first effect, but the second effect is related in a qnantitative way to the convective flow velocity The higher this velocity is, the thinner will be the diffusion layer and the larger the concentration gradients and diffusional fluxes. 

Each of the particles of Red produced in the chemical reaction will, after some (mean) time t, have been reconverted to A. Hence, when the current is anodic, only those particles of Red will be involved in the electrochemical reaction which within their own lifetime can reach the electrode surface by diffusion. This is possible only for particles produced close to the surface, within a thin layer of electrolyte called the reaction layer. Let this layer have a thickness 5,.. As a result of the electrochemical reaction, the concentration of substance Red in the reaction layer will vary from a value Cg at the outer boundary to the value Cg right next to the electrode within the layer a concentration gradient and a diffusion flux toward the surface are set up. 

It is a special feature of this diffusion situation that substance Red is produced by the chemical reaction, all along the diffusion path (i.e., sources of the substance are spatially distributed). For this reason the diffusion flux and the concentration gradient are not constant but increase (in absolute values) in the direction toward the surface. The incremental diffusion flux in a layer of thickness dx [ dJJdx)dx or -D (f-cldx ) dx] should be equal to the rate, v dx, of the chemical reaction in this layer. Hence, we have... 

Passivation phenomena on the whole are highly multifarious and complex. One must distinguish between the primal onset of the passive state and the secondary phenomena that arise when passivation has already occurred (i.e., as a result of passivation). It has been demonstrated for many systems by now that passivation is caused by adsorbed layers, and that the phase layers are formed when passivation has already been initiated. In other cases, passivation may be produced by the formation of thin phase layers on the electrode surface. Relatively thick porous layers can form both before and after the start of passivation. Their effects, as a rule, amount to an increase in true current density and to higher concentration gradients in the solution layer next to the electrode. Therefore, they do not themselves passivate the electrode but are conducive to the onset of a passive state having different origins. 

MIC depends on the complex structure of corrosion products and passive films on metal surfaces as well as on the structure of the biofilm. Unfortunately, electrochemical methods have sometimes been used in complex electrolytes, such as microbiological culture media, where the characteristics and properties of passive films and MIC deposits are quite active and not fully understood. It must be kept in mind that microbial colonization of passive metals can drastically change their resistance to film breakdown by causing localized changes in the type, concentration, and thickness of anions, pH, oxygen gradients, and inhibitor levels at the metal surface during the course of a... 

The percutaneous absorption picture can be qualitatively clarified by considering Fig. 3, where the schematic skin cross section is placed side by side with a simple model for percutaneous absorption patterned after an electrical circuit. In the case of absorption across a membrane, the current or flux is in terms of matter or molecules rather than electrons, and the driving force is a concentration gradient (technically, a chemical potential gradient) rather than a voltage drop [38]. Each layer of a membrane acts as a diffusional resistor. The resistance of a layer is proportional to its thickness (h), inversely proportional to the diffusive mobility of a substance within it as reflected in a... 

A stagnant diffusion layer is often assumed to approximate the effect of aqueous transport resistance. Figure 4 shows a membrane with a diffusion layer on each side. The bulk solutions are assumed to be well mixed and therefore of uniform concentrations cM and cb2. Adjacent to the membrane is a stagnant diffusion layer in which a concentration gradient of the solute may exist between the well-mixed bulk solution and the membrane surface the concentrations change from Cm to c,i for solution 1 and from cb2 to cs2 for solution 2. The membrane surface concentrations are cml and cm2. The membrane has thickness hm, and the aqueous diffusion layers have thickness ht and h2. 

In Eq. (41), the concentration gradient is expressed as a difference between the surface concentration, Cm, and the bulk concentration, CHS), divided by the diffusion layer thickness, 8. If sink dissolution conditions are assumed (Cb 0) and the solid has a uniform density (p = m/V), then Eq. (42) can be derived. 

Early investigators assumed that this so-called diffusion layer was stagnant (Nernst-Whitman model), and that the concentration profile of the reacting ion was linear, with the film thickness <5N chosen to give the actual concentration gradient at the electrode. In reality, however, the thin diffusion layer is not stagnant, and the fictitious t5N is always smaller than the real mass-transfer boundary-layer thickness (Fig. 2). However, since the actual concentration profile tapers off gradually to the bulk value of the concentration, the well-defined Nernst diffusion layer thickness has retained a certain convenience in practical calculations. 

In a stagnant solution, free convection usually sets in as a density gradient develops at the electrode upon passing current. The resulting convective velocity, which is zero at the wall, enhances the transfer of ions toward the electrode. At a fixed applied current, the concentration difference between bulk and interface is reduced. For a given concentration difference, the concentration gradient of the reacting species at the electrode becomes steeper (equivalent to a decrease of the Nernst layer thickness), and the current is thereby increased. 

The rate of diffusion of a substance is influenced by several factors (see Table 2.1). It is proporhonal to the concentration gradient the permeability of the membrane and the surface area of the membrane. For example, as the permeability of the membrane increases, the rate of diffusion increases. It is inversely proporhonal to the molecular weight of the substance and the thickness of the membrane. Larger molecules diffuse more slowly. 

In order to simplify the situation, we assume that our porous sample under investigation covers the bottom of an open straight-walled can and fills it to a height d (Figure 1). Such a sample will exhibit the same areal exhalation rate as a free semi-infinite sample of thickness 2d, as long as the walls and the bottom of the can are impermeable and non-absorbant for radon. A one-dimensional analysis of the diffusion of radon from the sample is perfectly adequate under these conditions. To idealize the conditions a bit further we assume that diffusion is the only transport mechanism of radon out from the sample, and that this diffusive transport is governed by Fick s first law. Fick s law applied to a porous medium says that the areal exhalation rate is proportional to the (radon) concentration gradient in the pores at the sample-air interface... 

The diffusion layer theory, illustrated in Fig. 15B, is the most useful and best-known model for transport-controlled dissolution. The dissolution rate here is controlled by the rate of diffusion of solute molecules across a diffusion layer of thickness h, so that kT kR in Eq. (40), which simplifies to kx = kT. With increasing distance, x, from the surface of the solid, the concentration, c, decreases from cs at x = 0 to cb at x = h. In general, c is a nonlinear function of x, and the concentration gradient dddx becomes less steep as x increases. The hyrodynamics of the dissolution process has been fully discussed by Levich [104]. In a stirred solution, the flow velocity of the liquid dissolution medium increases from zero at x = 0 to the bulk value at x = h. 

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