BET ISOTHERM

Brunauer, Emmet, and Teller have worked out a model for multilayer adsorption. They assumed that the first step in the adsorption is

where K1 is the equilibrium constant, 1 is the fraction of the surface sites covered by a single molecule, and v is the fraction of vacant sites. Next they assumed that additional molecules sit on top of one another to form a variety of multilayer. They interpreted the process as a sequence of chemical reactions, each with an appropriate equilibrium constant :

where the symbol A3S indicates a surface site that has a stack of three A molecules piled upon it. The i is the fraction of sites on which the stack of A molecules is i layers deep. The interaction between the first A molecule and the surface site is unique, depending on the particular nature of the A molecule and the surface. However, when the second A molecule sits on the first A molecule, the interaction cannot be very different from the interaction of two A molecules in the liquid ; the same is true when the third sits on the second. All of these processes except the first can be regarded as being essentially equivalent to liquefaction, and so they should have the same equilibrium constant, K. Thus the BET treatment assumes that

where K is the equilibrium constant for the reaction A(g) A(liquid). Then

where po is the equilibrium vapor pressure of the liquid. We can use the equilibrium conditions to calculate the values of the various i . We have

Combining the first two we have,

Repeating the operation, we find

The sum of all these fractions must be equal to unity :

In the second writing we replaced i by its equal from Kp = x, this becomes

If we temporarily set

If we now assume that the process can go on indefinitely, then n , and the series is simply the expansion of Thus

Using the equilibrium condition for the first adsorption, we find constant, c = K1/K; then

We define a new

And equation

become

become

Let N be the total number of molecules adsorbed per unit mass of adsorbent and cs be the total number of surface sites per unit mass. Then cs1 is the number of sites carrying one molecule, cs2 is the number carrying two molecules, and so on. Then

From

we have

this brings N to the form

We recognize this series as the derivative of the earlier one :

Using this result in the expression for N, we obtain

. If the entire surface were

covered with a monolayer, then Nm molecules would be adsorbed ; Nm = cs and

Using the value for 1 from equation

this become

The amount adsorbed is usually reported as the volume of the gas adsorbed, measured at STP. The volume is, of course, proportional to N so we have N /Nm = v/vm , or

Recalling that x = Kp and that K = 1/po, we have finally the BET isotherm :

The volume, v, is measured as a function of p. From the data we can obtain the value of Vm and c. Note that when p = po, the equation has a singularity and v . This accounts for the steep rise of the isotherm as the pressure approaches po . To obtain the constants c and Vm we multiply both sides of

by (po - p)/p :

Next we take the reciprocal of both sides :