Penurunan Persamaan BET

1. Langkah Pertama dalam Adsorpsi

r ads = kads.qv.p
r des = kdes.q1
      A(g) + S             AS   K1=q1/qvp

           K1 : the equilibrium constant, first ads layer,
           q1: the fraction of the suface sites covered by a single molecule,
           qv: the fraction of vacant sites.
  The other step (except the first step)
  A(g) + AS   A2S    K2=q2/q1p
  A(g) + A2S                 A3S    K3=q3/q2p
  A(g) + An-1S               AnS    Kn=qn/qn-1p

All of these processes except the first can be regarded as being 
essentially equivalent to liquefaction.

K2 = K3 = K4 = •••• = Kn = K

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

and,  K=1/Po  (Po is the equilibrium vapor pressure of the liquid)
  
2. We can use the equilibrium conditions to calculate the values of the
various qi. We have

 q2 = q1Kp,
 q3 = q2Kp,
 q4 = q3Kp •••.

Combining the first two we have, q3 = q1 (Kp)2. Repeating the 
operation, we find

qi = q1 (Kp)i-1 •••••••••••••••••••••••••••• eq.(1)

The sum of all these fractions must be equal to 
unity:
  
      1 = qv + ∑qi = qv + ∑q1(Kp)i-1
 From Eq.(1), if we temporarily set Kp=x,

1 = qv + q1(1 + x + x2 + x3 + ••• )

i ®¥, the series is simply the expansion of

1 + x + x2 + x3 + ••• = 1/(1-x)
 Thus,           
         1 = qv + 1q1/(1-x) ••••••••••••••••••••••• eq.(2)

Using the equilibrium condition for the first adsorption,

           qv = q1/K1p

   We define a new constant, c = K1/K.  and Kp =x or then

           qv = q1/cx

   And Eq.(2) becomes

1 = q1(1/cx + 1/(1-x)) ®         q1 = cx(1-x)/{1 + (c-1)x} ••••••••••••• eq.(3)

3) 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.
 csq1 : the number of sites carrying one molecule
 csq2 : the number of sites carrying two molecules, and so 
on.
     N = cs(1q1 + 2q2 + 3q3   + ••• ) = cs∑iqi
-       From Eq.(1) we have qi = q1 (Kp)i-1; this brings N to the 
form
     N = csq1 ∑ixi-1 = csq1(1 + 2x + 3x2 + •••)
Here, 
1 +2x + 3x2 + •••  = (d/dx)(1 + x + x2 + x3 + •••)
                 = (d/dx){1/(1-x)} = 1/(1-x)2
-       Using this result in the expanssion for N, we obtain
           N = csq1/(1-x)2
4)  If the entire surface were covered with a monolayer, then N m
molecules would be adsorbed; Nm = cs and
        

           N = Nmq1/(1-x)2

-       The value for q1 from Eq.(3), this becomes

     N = Nmcx/[(1-x)(1 + (c-1)x)]

-       Here,  N/Nm = v/vm

     v = vmcx/[(1-x)(1 + (c-1)x)]

   And, x = Kp , K=1/Po , we have finally the BET equation;

     \ v = vmcp/[(po-p)(1 + (c-1)(p/po)]
p 1 (c  1) p
 
V ( p  p ) Vm c
0
Vm c p 0
BET Equation
        ( intercept ; 1/vmc,  slope ; (c-1)/vmc)

N: Avogadro's number, s: adsorption cross section, V: molar volume of 
adsorbent gas a: weight of sample solid

Yang perlu diperhatikan:
1.Adsorpsi  fisisorpsi
2.Harga C harus positif c = K1/K ataupun