8)(!g& 1
8tep : ; <ass transfer !diffusion& of the reactants from the bul' fluid to the external surface of the catalyst pellet 8tep * ; =iffusion of the reactant from the pore mouth through the catalyst pores to the intermediate vicinity of the internal catalytic surface 8tep ( ; Adsorption of reactant !e.g., A& onto the catalyst surface 8tep % ; .eaction on the surface of the catalyst !e.g., A , 2& 8tep # ; =esorption of the products !e.g., 2& from the surface 8tep > ; =iffusion of the products from the interior of the pellet to the pore mouth at the external surface 8tep ? ; <ass transfer of the products from the external pellet surface to the bul' fluid Important Note: .eactions are not cataly ed over the entire surface but only at certain active sites or centers that result from unsaturated atoms in the surface. An active site is a point on the surface that can form strong chemical bonds with an adsorbed atom or molecule.
The adsorption step: In this step, reactant !A& combines with the active site !denoted by the letter 8& and forms the complex A.8 as follows@
A + 8 A 8
!:$.:&
In obtaining the rate law for the rate of adsorption, reaction in !:$.:& can be treated as elementary reactions. .ate of attachment of the molecules of A to the surface 5umber of collisions that the molecules of A ma'e with the surface !"artial pressure of A& x !Concentration of vacant site& !"A& x !C7& where "A is the partial pressure of A in the gas phase, and C 7 is the molar concentration of vacant sites per unit mass of catalyst !in molAg cat&, which is defined as the number of vacant sites per unit mass of catalyst divided by AvogadroBs number. .ate of attachment / 'A"AC7 where 'A is the constant of proportionality for the attachment process. .ate of detachment of the molecules of A from the surface !assuming as a first4order process& Concentration of sites occupied by the molecules A.8 !i.e., CA.8& .ate of detachment / ' ;ACA.8 !:$.(& where ' ;A is the constant of proportionality for the detachment process. Combining !:$.*& and !:$.(&, the net rate of adsorption !rA=& can be written as follows@ rA= / 'A"AC7 ; ' ;ACA.8 C A 8 rA= = ' A "A C 7 C A C t = C 7 + C A 8 !:$.%& Introducing the adsorption e3uilibrium constant CA !/ 'A A';A& in !:$.%&, we get the following@ !:$.*&
!:$.#&
If A is the only material adsorbed on the catalyst, the active site balance gives the following@ !:$.>&
where Ct is the total molar concentration of active sites per unit mass of catalyst !in molAg cat& defined as the number of active sites per unit mass of catalyst divided by AvogadroBs number. At e3uilibrium, the net rate of adsorption e3uals ero. That is, r A= / $. Therefore !:$.#& gives the following@
( C A8 ) e3m = C A "A C 7
Combining !:$.>& and !:$.?& and eliminating C7, we get
!:$.?&
( C A8 ) e3m =
C A "A C t : + C A "A
E3uation !:$.D& is an adsorption isotherm, 'nown as !:$.D&, we can get the following lineari ed e3uation@
( C A8 ) e3m
"A
: : "A + Ct C ACt
!:$.E&
Fet us now consider the dissociative adsorption reaction in which the molecule A* dissociates upon adsorption onto active sites as shown below@
A * + *8 *A 8
The net rate of adsorption !rA=& for this case would be
C* * * A 8 rA= = ' A "A C * ' C = ' " C 7 4 A A 8 A A 7 CA
!:$.:$&
At e3uilibrium,
( C A 8 ) e3m
= C A "A C 7
!:$.::&
( C A8 ) e3m =
C A "A C t : + C A "A
!:$.:*&
E3uation !:$.:*& is the angmuir Isotherm for dissociative adsorption. .earranging !:$.:*&, we can get the following lineari ed e3uation@
( C A8 ) e3m
"A
: Ct
"A +
: C A Ct
!:$.:(&
"#ercise $%!$: Tabulated data were gathered during adsorption of hydrogen on powdered copper at *#oC. =etermine if the data fit the Fangmuir isotherm given by !:$.D& or !:$.:*&.
Increasing pressure, "H* !torr& (.*# D.E$ :?.># (>.* ?%.# *$%.D CH*.8 x :$* !g molA g Cu& $.##E $.?>: $.E%: :.*:* :.*D: :.%?: =ecreasing pressure, "H* !torr& %#.: *:.# :$.># #.%$ *.E# :.?$ CH*.8 x :$* !g molA g Cu& :.:>$ $.EE# $.D$$ $.>#E $.#>% $.%>%
"#ercise $%!&: 8how that the adsorption isotherm of A in the presence of adsorbent 2 is given by
( C A8 ) e3m =
when the adsorption of both A and 2 and desorptions are first4order processes, and both A and 2 are adsorbed as molecules.
The surface reaction step: )nce a reactant had been adsorbed onto the surface, it is capable of reacting in a number of ways to form the reaction product, which are the single'site mechanism, dual'site mechanism, and the reaction bet(een adsorbed molecule and a molecule in the gas'phase. :. Single site. In single'site mechanism, only the site on which the reactant is adsorbed is involved in the reaction. Gor example, an adsorbed molecule of A may isomeri es !or perhaps decompose& directly on the site to which it is attached.
A 8 28
!:$.:%&
An example is the n4pentene yielding i4pentene on Al *)( surface. Assuming elementary reaction mechanism, the surface reaction rate can be given by C 28 r8 = ' 8 C A 8 C 8
!:$.:#&
where C8 is the surface reaction e3uilibrium constant given by C8 !/ '8 A' ;8&. *. Dual site. The surface reaction may be a dual4site mechanism in which the adsorbed reactant interacts with another site !either unoccupied or occupied& to form the product. Gor example, adsorbed A may react with an adHacent vacant site to yield a vacant site and a site on which the product is adsorbed.
A 8 + 8 28 + 8
!:$.:>&
!:$.:?&
The single4site or dual4site mechanisams described above are referred to as Fangmuir4 Hinshelwood 'inetics. (. Eley4.ideal mechanism is the reaction between an adsorbed molecule and a molecule in the gas4phase.
A 8 + 2! g & C 8
!:$.:D&
The corresponding surface reaction rate can be given by CC8 r8 = ' 8 C " A 8 2 C 8
!:$.:E&
The desorption step: In each of the cases discussed above, the products of the surface reaction adsorbed on the surface are subse3uently desorbed into the gas phase.
28 2 + 8
!:$.*$&
.ate of attachment / ' 2"2C7 The net rate of desorption !r=& can therefore be written as follows@ C 28 r= = ' 4 2C 2.8 ' 2 "2C 7 = ' 2 C "2C 7 2 where the desorption e3uilibrium constant C2 !/ '2 A';2&. The )ate imiting Step: -hich 8tep Has the Fargest .esistanceI Hydrodemethylation of toluene: 8tep :@ Adsorption of toluene !T& on an active site !8& of the catalyst surface
T!g& + 8 T 8
!:$.*:&
!:$.**&
8tep *@ Toluene adsorbed on the active site reacts with hydrogen in the gas4phase to produce ben ene !2& adsorbed on the surface and methane !<& in the gas4phase.
H * !g& + T 8 2 8 + <!g&
C 28 "< r8 = ' 8 "H * C T 8 C 8 8tep (@ 2en ene is then desorbed from the surface.
2 8 2!g& + 8
!:$.*(&
C 28 r= = ' 2 C "2C 7 2 If the reaction is surface4reaction limiting then !4r8& J rA= and !4r8& J r=. Therefore, '8 JJ 'T and '8 JJ '2. Thus, we can set rA= A 'T K $ and r= A '2 K $. The net rate of reaction is indeed given by !:$.*(&.
!:$.*%&
-e need to determine CT.8. and C2.8 of !:$.*(&, for which we will use r A= A 'T K $ and r= A '2 K $. rA= A 'T K $ gives C T 8 = C T "T C 7 r= A '2 K $ gives C 28 = C 2 "2C 7 8ite balance gives C t = C 7 + C T 8 + C 28 Combining !:$.*#&, !:$.*>& and !:$.*?&, we get C 7 = C t A!: + C T "T + C 2 "2 & Lsing !:$.*#&, !:$.*>& and !:$.*D&, we can rewrite !:$.*(& as follows@ !:$.*D& !:$.*#& !:$.*>& !:$.*?&
C t ' 8 C T "H * "T "< "2 A C e Ct "< "2 = '8 C T "H * "T C C AC :+ C " + C " = : + C T "T + C 2 "2 T 8 2 T T 2 2 'C T "H * "T "< "2 A C e = : + C T "T + C 2 "2
where ' / Ct '8 and Ce /CTC8 A C2. If the reverse surface reaction is neglected, we get r8 = 'C T "H * "T : + C T "T + C 2 "2
!:$.*E&
"#ercise $%!*: =etermine the rate4law parameters ', C2 and CT using the data tabulated below@
.un ( % > ? E :$ :* :( :% :# r8 x :$:$ !g molAg cat. s& %:.> :E.? :?.: ?:.D *D%.$ %?.$ ::?.$ :*?.$ :(:.$ :((.$ "T !atm& : : : : : $.# # :$ :# *$ "H* !atm& : : : : % : : : : : "2 !atm& : % # $ $ $ $ $ $ $
.ef@ Chapter > of H.8 . Gogler, Elements of .eaction Engineering !*nd edition& 7