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) he rate of desorption is taken to proportional to the a!ount present in that layer. he heat of adsorption for all layers e#cept the first layer is assu!ed to be equal to the heat of liquefaction of the adsorption gas.

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Derivation of equation
1) he first step in the adsorption $%g) & ' $' (1)1*vp r ads = kads.v.p r des = kdes.1

(1 + the equilibriu! constant, first ads layer, 1+ the fraction of the suface sites covered by a single !olecule, v+ the fraction of vacant sites. he other step %e#cept the first step) $%g) & $' $%g) & $2' $%g) & $n,1' , $2' $3' $n' (2)2*1p (3)3*2p (n)n*n,1p

$ll of these processes e#cept the first can be regarded as being essentially equivalent to liquefaction.

(2 ) (3 ) (4 ) ---- ) (n ) (
%( is the equilibriu! constant for the reaction $%g) and, ()1*.o %.o is the equilibriu! vapor pressure of the liquid) $%liquid) )

2) /e can use the equilibriu! conditions to calculate the values of the various i. /e have 2 ) 1(p, 3 ) 2(p, 4 ) 3(p ---. , 0o!bining the first t1o 1e have, 3 ) 1 %(p)2. 2epeating the operation, 1e find i ) 1 %(p)i,1 ---------------------------- eq.%1) , he su! of all these fractions !ust be equal to unity+ 1 ) v & i ) v & 1%(p)i,1

Fro! 3q.%1), if 1e te!porarily set Kp=x, 1 ) v & 1%1 & # & #2 & #3 & --- )

i , the series is si!ply the e#pansion of 1 & # & #2 & #3 & --- ) 1*%1,#) hus, 1 ) v & 11*%1,#) ----------------------- eq.%2) , 5sing the equilibriu! condition for the first adsorption, %buktikan4, taylor)

v ) 1*(1p
/e define a ne1 constant, c ) (1*(. and (p =x or then

v ) 1*c#
$nd 3q.%2) beco!es 1 ) 1%1*c# & 1*%1,#)) 1 ) c#%1,#)*61 & %c,1)#7 ------------- eq.%3)

3) 8et 9 be the total nu!ber of !olecules adsorbed per unit !ass of adsorbent and cs be the total nu!ber of surface sites per unit !ass. cs1 + the nu!ber of sites carrying one !olecule cs2 + the nu!ber of sites carrying t1o !olecules, and so on. 9 ) cs%11 & 22 & 33 & --- ) ) csii , Fro! 3q.%1) 1e have i ) 1 %(p)i,1: this brings 9 to the for! 9 ) cs1 i#i,1 ) cs1%1 & 2# & 3#2 & ---) Here,

1 &2# & 3#2 & --- ) %d*d#)%1 & # & #2 & #3 & ---) ) %d*d#)61*%1,#)7 ) 1*%1,#)2 , 5sing this result in the e#panssion for 9, 1e obtain 9 ) cs1*%1,#)2 4) ;f the entire surface 1ere covered 1ith a !onolayer, then 9 ! !olecules 1ould be adsorbed: 9! ) cs and 9 ) 9!1*%1,#)2 , he value for 1 fro! 3q.%3), this beco!es 9 ) 9!c#*<%1,#)%1 & %c,1)#)= , Here, 9*9! ) v*v! v ) v!c#*<%1,#)%1 & %c,1)#)= $nd, # ) (p , ()1*.o , 1e have finally the >3 equation:

v ) v!cp*<%po,p)%1 & %c,1)%p*po)=

p 1 (c 1) p = + V ( p p ) Vm c Vm c p 0
0

Persamaan BET

BET Equation
% intercept : 1*v!c, slope : %c,1)*v!c)

N: Avogadro's number, s: adsorption cross section, V: molar volume of adsorbent gas a: eig!t of sample solid

"ang perlu diper!ati#an: 1$ Adsorpsi fisisorpsi %$ &arga ' !arus positif

c ) (1*( ataupun

1 ) v & 1 & 2 & 3 & 4 & . . . 1 ) v & i ) v & 1%(p)i,1 9 be the total nu!ber of !olecules adsorbed, and c s be the total nu!ber of surface sites. cs1 + the nu!ber of sites carrying one !olecule cs2 + the nu!ber of sites carrying t1o !olecules, and so on. 9 ) cs%11 & 22 & 33 & --- ) ) csii