Gradient substances

Diffusion. Mass transfer by diffusion is the natural transport or movement of a substance under the influence of a gradient of chemical potential, that is, due to the concentration gradient-, substances move from regions of high concentration to regions of low concentration in order to minimize or eliminate concentration differences. Diffusion is perhaps the most widely studied means of mass transport. 

Fick s law of diffusion A law relating the rate of diffusion of a substance in a given direction to the gradient of its concentration. 

Ac Che limic of Knudsen screaming Che flux relacions (5.25) determine Che fluxes explicitly in terms of partial pressure gradients, but the general flux relacions (5.4) are implicic in Che fluxes and cheir solution does not have an algebraically simple explicit form for an arbitrary number of components. It is therefore important to identify the few cases in which reasonably compact explicit solutions can be obtained. For a binary mixture, simultaneous solution of the two flux equations (5.4) is straightforward, and the result is important because most experimental work on flow and diffusion in porous media has been confined to pure substances or binary mixtures. The flux vectors are found to be given by... 

In general, therefore, the surface flux of each substance is linearly related Co all the concentration gradients in the adjacent bulk phase. The coefficients in this linear relation depend on the bulk phase concentrations,... 

Let us first consider experiments without composition gradients. These are permeability measurements, in which flow is induced by a pressure gradient Consider first the flow of pure substance 1, setting x = 1, = 0 and... 

Under equiUbrium or near-equiUbrium conditions, the distribution of volatile species between gas and water phases can be described in terms of Henry s law. The rate of transfer of a compound across the water-gas phase boundary can be characterized by a mass-transfer coefficient and the activity gradient at the air—water interface. In addition, these substance-specific coefficients depend on the turbulence, interfacial area, and other conditions of the aquatic systems. They may be related to the exchange constant of oxygen as a reference substance for a system-independent parameter reaeration coefficients are often known for individual rivers and lakes. 

Finally, it is to be expected that the evaporation coefficient of a very stable compound, such as alumina, which has a large heat of sublimation resulting from the decomposition into the elements, will be low. Since the heat of evaporation must be drawn from the surface, in die case of a substance widr a low thermal conductivity such as an oxide, the resultant cooling of the surface may lead to a temperature gradient in and immediately below the surface. This will lower die evaporation rate compared to that which is calculated from the apparent, bulk, temperature of the evaporating sample as observed by optical pyromeuy, and thus lead to an apparently low free surface vaporization coefficient. This is probably die case in the evaporation of alumina in a vacuum. 

Diffusion The mixing of substances by molecular motion to equalize a concentration gradient. Applicable to gases, fine aerosols and vapors. (See Brownian diffusion.)... 

The Fourier law gives the rate at which heat is transferred by conduction through a substance without mass transfer. This states that the heat flow rate per unit area, or heat flux, is proportional to the temperature gradient in the direction of heat flow. The relationship between heat flux and temperature gradient is characterized by the thermal conductivity which is a property of the substance. It is temperature dependent and is determined experimentally. 

Let [1], [2], [8] be any three modifications of a substance which can exist together in equilibrium at a triple point, and let t i, r2, r3 be their specific volumes su s2, s3, their entropies per unit mass. The gradients of the p-T curves at the triple point are given by the latent-heat equations ... 

The following factors affect net diffusion of a substance (1) Its concentration gradient across the membrane. Solutes move from high to low concentration. (2) The electrical potential across the membrane. Solutes move toward the solution that has the opposite charge. The inside of the cell usually has a negative charge. (3) The permeability coefficient of the substance for the membrane. (4) The hydrostatic pressure gradient across the membrane. Increased pressure will increase the rate and force of the collision between the molecules and the membrane. (5) Temperature. Increased temperature will increase particle motion and thus increase the frequency of collisions between external particles and the membrane. In addition, a multitude of channels exist in membranes that route the entry of ions into cells. 

The second most widely used detector in HPLC is the differential refractometer (RI). Being a bulk property detector, the RI responds to all substances. As noted in Table 3 the detection limits are several orders of magnitude higher than obtained with the UV detector. Thus, one turns to the RI detector in those cases in which substances are non-UV active, e.g. lipids, prostaglandins. In addition, the RI detector finds use in preparative scale operation. Finally, relative to the UV detector, the RI is significantly more temperature and flow sensitive and cannot be used in gradient elution. 

Adsorption chromatography using small particle silica or alumina has also been employed in the separation of biologically meaningful substances. Phospholipids, for example, have been separated on silica (38). One of the big problems for such substances is detection, since many of the compounds are not U.V. active. Generally, the refractive index detector is employed for isocratic operation, and the moving wire detector for gradient operation. Formation of U.V.-active derivatives is also possible (39). 

Certain chemical substances have been known for many years to uncouple oxidation firm phosphorylation and to inhibit active transport, and for this reason they are named imcoupling agerrts. They are beheved to act by rendering the membrane permeable to protons hence short-circuiting the potential gradient or protonmotive force. 

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