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The process by which certain porous solids bind large numbers of molecules to their surfaces is known as adsorption Not only does it serve as a separation process, but it is also a vital part of catalytic-reaction processes As a separation process, adsorption is used most often for removal of low-concentrationimpurities and pollutants from fluid streams It is also the basis for chromatographyIn surface-catalyzedreactions, the initial step is adsorption of reactant species; the final step is the reverse process, desorption of product species Since most industrially important reactions are catalytic, adsorption plays a fundamental role in reaction engineering The nature of the adsorbing surface is the determining factor in adsorption The molecular characterization of solid surfaces is not yet fully developed; however, current knowledge allows a helpful description To be useful as an adsorbent, a solid must present a large surface area per unit mass (up to 1500 m2 per gram) This can only be achieved with porous solids such as activated carbon, silica gels, aluminas, and zeolites, which contain many cavities or pores with diameters as small as a fraction of a nanometer Surfaces of such solids are necessarily irregular at the molecular level, and they contain sites of particular attraction for adsorbing molecules If the sites are close together, the adsorbed molecules may interact with one another; if they are sufficiently dispersed, the adsorbed molecules may interact only with the sites Depending upon the strength of the forces binding them to the sites, these adsorbate molecules may be mobile or fixed in position The relatively weak electrostatic, induction, and dispersion forces discussed in Sec 161 favor mobility and result in physical adsorption On the other hand, much stronger quasichemical forces can act to fix molecules to the surface, promoting chernisorption Although adsorption may be classified in several ways, the usual distinction is between physical adsorption and chemisorption Based on the strength of the binding forces, this division is observed experimentally in the magnitudes of the heat of adsorption In the adsorption of gases, the number of molecules attracted to a solid surface depends on conditions in the gas phase For very low pressures, relatively few molecules are adsorbed, and only a fraction of the solid surface is covered As the gas pressure increases at a given temperature, surface coverage increases When all sites become occupied, the adsorbed molecules are said to form a monolayer Further increase in pressure promotes multilayer adsorption It is also possible for multilayer adsorption to occur on one part of a porous surface when vacant sites still remain on another part The complexities of solid surfaces and our inability to characterize exactly their interactions with adsorbed molecules limits our understanding of the adsorption process It does not, however, prevent development of an exact thermodynamic description of adsorption equilibrium, applicable alike to physical adsorption and chemisorption and equally to monolayer and multilayer adsorption The thermodynamic framework is independent of any particular theoretical or empirical description of material behavior However, in application such a description is essential, and meaningful results require appropriate models of behavior.

Listing 11-35 illustrates the use of the IS NULL operator In this example, all the columns in rows of the Customers table are returned in the ResultSet if the value of the State column in the row is NULL Listing 11-28 contains the DownRow() method that should be used to copy and display the ResultSet returned by Listing 11-35

<web-app> <!-- intervening elements omitted --> <security-constraint> <!-- contents omitted, see discussion on Authorization --> </security-constraint> <login-config> <auth-method>BASIC</auth-method> <realm-name>file</realm-name> </login-config> <!-- intervening elements omitted --> </web-app>

The details of the <security-constraint> element are left to the section on authorization, but for now, just know that this element allows you to control which parts of your application are subject to authentication

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The thermodynamictreatment of gasladsorbateequilibrium is in many respects analogous to that of vaporlliquid equilibrium However, the definition of a system to which the equations of thermodynamics apply presents a problem The force field of the solid adsorbent influences properties in the adjacent gas phase, but its effect decreases rapidly with distance Thus the properties of the gas change rapidly in the immediate neighborhood of the solid surface, but they do not change abruptly A region of change exists which contains gradients in the properties of the gas, but the distance into the gas phase that the solid makes its influence felt cannot be precisely established This problem is circumvented by a construct devised by J W Gibbs Imagine that the gas-phase properties extend unchanged up to the solid surface Differences between the actual and the unchanged properties can then be attributed to a mathematical surface, treated as a twodimensional phase with its own thermodynamic properties This provides not only a precisely defined surface phase to account for the singularities of the interfacial region, but it also extracts them from the three-dimensional gas phase so that it too may be treated precisely The solid, despite the influence of its force field, is presumed inert and not otherwise to participate in the gasladsorbate equilibrium Thus for purposes of thermodynamic analysis the adsorbate is treated as a two-dimensional phase, inherently an open system because it is in equilibrium with the gas phase The fundamental property relation for an open P V T system is given by Eq (112):

try { String query = new String ("SELECT " + "FirstName, LastName, Street, City, State, ZipCode, Sales " + "FROM Customers " + "WHERE State IS NULL "); DataRequest = DatabasecreateStatement(); Results = DataRequestexecuteQuery (query); DisplayResults (Results); DataRequestclose(); }

14:

An analogous equation may be written for a two-dimensional phase The only difference is that pressure and molar volume are not in this case appropriate variables Pressure is replaced by the spreading pressure IT,and the molar volume by the molar area a :

The Servlet API provides several methods on HttpServletRequest to interface with the container-managed authentication system, regardless of which method (basic, form, digest, or client certificate) is used These are shown in Table 14-1 These methods provide one way to build application-managed security on top of the existing security infrastructure of the Web tier We ll revisit these API methods in the section Container-Managed Authorization and the Concept of Roles with an example of how to integrate container-managed security elements into application-managed security Let s examine each of the four implementations of container-managed authentication in the Java EE Web tier

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