Langmuir equation equation

Next, let the example of vanadium, which, in the as-reduced condition, may contain a variety of impurities (including aluminum, calcium, chromium, copper, iron, molybdenum, nickel, lead, titanium, and zinc) be considered. Vanadium melts at 1910 °C, and at this temperature it is considerably less volatile than many of the impurity metals present in it. The vapor pressure of pure vanadium at this temperature is 0.02 torr, whereas those of the impurity elements in their pure states are the following aluminum 22 torr calcium 1 atm, chromium 6 torr copper 23 torr iron 2 torr molybdenum 6 1CT6 torr nickel 1 torr lead 1 torr titanium 0.1 torr and zinc 1 atm. However, since most of these impurities form a dilute solution in vanadium, their actual partial pressures over vanadium are considerably lower than the values indicated. Taking this into account, the vaporization rate, mA, of an element A (the evaporating species) can be approximated by the following free evaporation equation (Langmuir equation) ... 

Although still used the Langmuir equation is only of limited value since in practice surfaces are energetic inhomogeneous and interactions between adsorbed species often occur. 

Assume that an aqueous solute adsorbs at the mercury-water interface according to the Langmuir equation x/xm = bc/( + be), where Xm is the maximum possible amount and x/x = 0.5 at C = 0.3Af. Neglecting activity coefficient effects, estimate the value of the mercury-solution interfacial tension when C is Q.IM. The limiting molecular area of the solute is 20 A per molecule. The temperature is 25°C. 

Assume that a salt, MX (1 1 type), adsorbs at the mercury-water interface according to the Langmuir equation ... 

If the Langmuir equation is obeyed, combination of Eqs. XI-4 and XI-13 gives the von SzysTkowski equation [24,25]... 

The Langmuir equation (Eq. XI-4) applies to many systems where adsorption occurs from dilute solution, but some interesting cases of sigmoid isotherms have been reported [54-56]. In several of these studies [54,55] the isotherms... 

Adsorption at a charged surface where both electrostatic and speciflc chemical forces are involved has been discussed to some extent in connection with various other topics. These examples are drawn together here for a brief review along with some more speciflc additional material. The Stem equation, Eq. V-19, may be put in a form more analogous to the Langmuir equation, Eq. XI-4 ... 

Dye adsorption from solution may be used to estimate the surface area of a powdered solid. Suppose that if 3.0 g of a bone charcoal is equilibrated with 100 ml of initially 10 Af methylene blue, the final dye concentration is 0.3 x 10 Af, while if 6.0 g of bone charcoal had been used, the final concentration would have been 0.1 x Qr M. Assuming that the dye adsorption obeys the Langmuir equation, calculate the specific surface area of the bone charcoal in square meters per gram. Assume that the molecular area of methylene blue is 197 A. ... 

The adsorption of the surfactant Aerosol OT onto Vulcan Rubber obeys the Langmuir equation [237] the plot of C/x versus C is linear. For C = 0.5 mmol/1, C/x is 100 mol/g, and the line goes essentially through the origin. Calculate the saturation adsorption in micromoles per gram. 

The preceding derivation, being based on a definite mechanical picture, is easy to follow intuitively kinetic derivations of an equilibrium relationship suffer from a common disadvantage, namely, that they usually assume more than is necessary. It is quite possible to obtain the Langmuir equation (as well as other adsorption isotherm equations) from examination of the statistical thermodynamics of the two states involved. 

This difference looks large enough to be diagnostic of the state of the adsorbed film. However, to be consistent with the kinetic derivation of the Langmuir equation, it was necessary to suppose that the site acted as a potential box and, furthermore, that a weak adsorption bond of ifi corresponding to 1 /tq was present. With these provisions we obtain... 

A variety of experimental data has been found to fit the Langmuir equation reasonably well. Data are generally plotted according to the linear form, Eq. XVn-9, to obtain the constants b and n from the best fitting straight line. The specific surface area, E, can then be obtained from Eq. XVII-10. A widely used practice is to take to be the molecular area of the adsorbate, estimated from liquid or solid adsorbate densities. On the other hand, the Langmuir model is cast around the concept of adsorption sites, whose spacing one would suppose to be characteristic of the adsorbent. See Section XVII-5B for an additional discussion of the problem. 

The basic assumption is that the Langmuir equation applies to each layer, with the added postulate that for the first layer the heat of adsorption Q may have some special value, whereas for all succeeding layers, it is equal to Qu, the heat of condensation of the liquid adsorbate. A furfter assumption is that evaporation and condensation can occur only from or on exposed surfaces. As illustrated in Fig. XVII-9, the picture is one of portions of uncovered surface 5o, of surface covered by a single layer 5, by a double-layer 52. and so on.f The condition for equilibrium is taken to be that the amount of each type of surface reaches a steady-state value with respect to the next-deeper one. Thus for 5o... 

Although the preceding derivation is the easier to follow, the BET equation also may be derived from statistical mechanics by a procedure similar to that described in the case of the Langmuir equation [41,42]. 

Equation XVII-70 bears a strong resemblance to the Langmuir equation (see Ref. 4)—to the point that it is doubtful whether the two could always be distinguished experimentally. An equivalent form obtained by Volmer [53] worked well for data on the adsorption of various organic vapors on mercury [54] (see Problem XVII-40). 

The rate of physical adsorption may be determined by the gas kinetic surface collision frequency as modified by the variation of sticking probability with surface coverage—as in the kinetic derivation of the Langmuir equation (Section XVII-3A)—and should then be very large unless the gas pressure is small. Alternatively, the rate may be governed by boundary layer diffusion, a slower process in general. Such aspects are mentioned in Ref. 146. 

Derive the general form of the Langmuir equation (Eq. XVII-11). 

The separate adsorption isotherms for gases A and B on a certain solid obey the Langmuir equation, and it may be assumed that the mixed or competitive adsorption obeys the corresponding form of the equation. 

Gas A, by itself, adsorbs to a of 0.02 at P = 200 mm Hg, and gas B, by itself, adsorbs tod = 0.02 at P = 20 mm Hg Tisll K in both cases, (a) Calculate the difference between (2a and (2b> the two heats of adsorption. Explain briefly any assumptions or approximations made, ib) Calculate the value for 6 when the solid, at 77 K, is equilibrated with a mixture of A and B such that the final pressures are 200 mm Hg each, (c) Explain whether the answer in b would be raised, lowered, or affected in an unpredictable way if all of the preceding data were the same but the surface was known to be heterogeneous. The local isotherm function can still be assumed to be the Langmuir equation. 

As a simple model of a heterogeneous surface, assume that 20% of it consists of sites of Q= 2.5 kcal/mol 45% of sites Q = 3.5 kcal/mol and the remainder, of sites of Q= 4.5 kcal/mol. Calculate Q(P, T) for nitrogen at 77 K and at 90 K, assuming the adsorption to follow the Langmuir equation with bo given by Eq. XVII-15. Calculate qsi for several 6 values and compare the result with the assumed integral distribution hinction. 

Because of the relatively strong adsorption bond supposed to be present in chemisorption, the fundamental adsorption model has been that of Langmuir (as opposed to that of a two-dimensional nonideal gas). The Langmuir model is therefore basic to the present discussion, but for economy in presentation, the reader is referred to Section XVII-3 as prerequisite material. However, the Langmuir equation (Eq. XVlI-5) as such,... 

Since in chemisorption systems it is reasonable to suppose that the strong adsorbent-adsorbate interaction is associated with specific adsorption sites, a situation that may arise is that the adsorbate molecule occupies or blocks the occupancy of a second adjacent site. This means that each molecule effectively requires two adjacent sites. An analysis [106] suggests that in terms of the kinetic derivation of the Langmuir equation, the rate of adsorption should now be... 

Some early observations on the catalytic oxidation of SO2 to SO3 on platinized asbestos catalysts led to the following observations (1) the rate was proportional to the SO2 pressure and was inversely proportional to the SO3 pressure (2) the apparent activation energy was 30 kcal/mol (3) the heats of adsorption for SO2, SO3, and O2 were 20, 25, and 30 kcal/mol, respectively. By using appropriate Langmuir equations, show that a possible explanation of the rate data is that there are two kinds of surfaces present, 5 and S2, and that the rate-determining step is... 

Equation (2.6) is the familiar Langmuir equation for the case when adsorption is confined to a monolayer. In practice B is an empirical constant and cannot be evaluated from the relationship in Equation (2.7). The question as to how well the Langmuir equation reproduces experimental isotherms will be dealt with in Chapter 4. 

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