Penjabaran BET

Derivation of BET(Brunauer-Emmett-Teller) Equation
- the most common method of measuring surface area
- based on multilayer adsorption (physical adsorption)
Assumption
1) For the first layer the rate of desorption is considered to be equal to
the rate of adsorption
2) Heat of adsorption is taken to be independent of coverage.
3) For layers beyond the first, the rate of adsorption is taken to be

proportional to the fraction of the latest layer still vacant.
4) The rate of desorption is taken to proportional to the amount present

in that layer.
5) The heat of adsorption for all layers except the first layer is
assumed to be equal to the heat of liquefaction of the adsorption gas.
Derivation of equation
1) The first step in the adsorption r ads = kads.θv.p
r des = kdes.θ1
A(g) + S AS K1=1/vp
K1 : the equilibrium constant, first ads layer,
1: the fraction of the suface sites covered by a single molecule,
v: the fraction of vacant sites.
The other step (except the first step)
A(g) + AS A2S K2=2/1p
A(g) + A2S A3S K3=3/2p
A(g) + An-1S AnS Kn=n/n-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 i. We have
2 = 1Kp, 3 = 2Kp, 4 = 3Kp •••.
- Combining the first two we have, 3 = 1 (Kp)2. Repeating the operation,

we find
i = 1 (Kp)i-1 •••••••••••••••••••••••••••• eq.(1)
- The sum of all these fractions must be equal to unity:
1 = v + i = v + 1(Kp)i-1
- From Eq.(1), if we temporarily set Kp=x,
1 = v + 1(1 + x + x2 + x3 + ••• )
i , the series is simply the expansion of
1 + x + x2 + x3 + ••• = 1/(1-x) (buktikan!, taylor)
Thus,
1 = v + 11/(1-x) ••••••••••••••••••••••• eq.(2)
- Using the equilibrium condition for the first adsorption,
v = 1/K1p
We define a new constant, c = K1/K. and Kp =x or then
v = 1/cx
And Eq.(2) becomes
1 = 1(1/cx + 1/(1-x))
 1 = 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.
cs1 : the number of sites carrying one molecule
cs2 : the number of sites carrying two molecules, and so on.
N = cs(11 + 22 + 33 + ••• ) = csii
- From Eq.(1) we have i = 1 (Kp)i-1; this brings N to the form
N = cs1 ixi-1 = cs1(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 = cs1/(1-x)2
4) If the entire surface were covered with a monolayer, then N m

molecules would be adsorbed; Nm = cs and
N = Nm1/(1-x)2
- The value for 1 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
  Persamaan BET
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
1 = v + 1 + 2 + 3 + 4 + 
1 = v + i = v + 1(Kp)i-1
N be the total number of molecules adsorbed, and c s be the total number of

surface sites.
cs1 : the number of sites carrying one molecule
cs2 : the number of sites carrying two molecules, and so on.
N = cs(11 + 22 + 33 + ••• ) = csii

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Derivation of BET(Brunauer-Emmett-Teller) Equation

- the most common method of measuring surface area

- based on multilayer adsorption (physical adsorption)

2) Heat of adsorption is taken to be independent of coverage.

3) For layers beyond the first, the rate of adsorption is taken to be

4) The rate of desorption is taken to proportional to the amount present

K1 : the equilibrium constant, first ads layer,

1: the fraction of the suface sites covered by a single molecule,

v: the fraction of vacant sites.

The other step (except the first step)

A(g) + AS A2S K2=2/1p

A(g) + A2S A3S K3=3/2p

A(g) + An-1S AnS Kn=n/n-1p

- All of these processes except the first can be regarded as being

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

2) We can use the equilibrium conditions to calculate the values of the

2 = 1Kp, 3 = 2Kp, 4 = 3Kp •••.

- Combining the first two we have, 3 = 1 (Kp)2. Repeating the operation,

i = 1 (Kp)i-1 •••••••••••••••••••••••••••• eq.(1)

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

i , the series is simply the expansion of

1 + x + x2 + x3 + ••• = 1/(1-x) (buktikan!, taylor)

1 = v + 11/(1-x) ••••••••••••••••••••••• eq.(2)

- Using the equilibrium condition for the first adsorption,

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

And Eq.(2) becomes

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

3) Let N be the total number of molecules adsorbed per unit mass of

cs1 : the number of sites carrying one molecule

cs2 : the number of sites carrying two molecules, and so on.

N = cs(11 + 22 + 33 + ••• ) = csii

- From Eq.(1) we have i = 1 (Kp)i-1; this brings N to the form

N = cs1 ixi-1 = cs1(1 + 2x + 3x2 + •••)

- Using this result in the expanssion for N, we obtain

4) If the entire surface were covered with a monolayer, then N m

- The value for 1 from Eq.(3), this becomes

- Here, N/Nm = v/vm

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

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

N be the total number of molecules adsorbed, and c s be the total number of

cs1 : the number of sites carrying one molecule

cs2 : the number of sites carrying two molecules, and so on.

N = cs(11 + 22 + 33 + ••• ) = csii

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