CP303 Set #10 (January-May 2012)

Catalysis and Catalytic Reactors

A catalyst is a substance that increases a reaction rate without itself being consumed in the reaction. In principle, all of a catalyst can be recovered unchanged at the end of a reaction. The energy released or absorbed by a chemical reaction is exactly the same whether a catalyst is present or not. A catalyst only affects the reaction rate. Catalysis is the occurrence, study, and use of catalysts and catalytic processes. Three main types of catalysis are Homogeneous Catalysis, Heterogeneous Catalysis and En yme Catalysis !which will be learned in C"#$%&. Homogeneous Catalysis: Homogeneous implies that the reaction ta'es place in solution !a homogeneous system&, with the soluble catalyst also in solution. The classic example is the catalysis of ester hydrolysis by hydrogen ion. CH(C)C*H# + H*) , CH(C))H + C*H#)H -ithout H+ the process is very slow and the rate depends only on ester concentration. .ate / ' 0CH(C)C*H#1 -ith H+, it is much more rapid and the cataly ed reaction is second order, that is, first order with respect to both ester and hydrogen ion concentration. .ate / 'c 0CH(C)C*H#1 0H+1 2y the definition of catalysis, 'c > ' Heterogeneous Catalysis: Heterogeneous catalysis is widely used in industrial manufacture of chemicals. The catalyst is usually in the solid phase and the reactants are either gaseous or li3uid. The gas or li3uid molecules bond temporarily to the atoms at the surface of the catalyst, which allows their internal bonds to brea' more rapidly or at a lower temperature. Catalytic Converter: In the automobile catalytic converter !a Cu or Cr oxide surface& cataly es the rapid decomposition of toxic and smog4producing nitrogen oxides in the exhaust to harmless nitrogen and oxygen gas. 5)x!g& 5*!g& + )*!g& A precious metal catalyst, platinum !"t&, palladium !"d& or rhodium !.h&, converts C) and )* in the exhaust stream to C)*. The Haber Synthesis of Ammonia: "robably the most important industrial process converts nitrogen gas and hydrogen to ammonia for use in fertili er. The reaction is exothermic !energetically favorable& but it is very slow. H* !g& + 5*!g& 5H(!g& H* molecules adhere readily to the surface of an iron metal catalyst and dissociate readily into H atoms which allows them to react rapidly with nitrogen gas. The reaction proceeds much faster at #$$ 6C than it would without the catalyst and ma'es the reaction an economically favourable process. Sulfuric Acid Production: "latinum !"t& or vanadium !7& oxide cataly e the production of 8)( from 8)*, a 'ey step in the manufacture of sulfuric acid. 8ulfuric acid is re3uired for so many applications that annual production of the acid was used as an index of industrial productivity. 8)*!g& + 9 )*!g&
7*)#

8)(!g& 1

Catalytic packed bed reactor

Steps in a heterogeneous catalytic reaction

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

!:$.D& angmuir Isotherm! .earranging

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

!:$.::&

Combining !:$.>& and !:$.::& and eliminating C7, we get

( 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 $.#>% $.%>%

: torr / : mm Hg / $.:(( "a / $.$$:(* atm

"#ercise $%!&: 8how that the adsorption isotherm of A in the presence of adsorbent 2 is given by

( C A8 ) e3m =

C A "A C t : + C A "A + C 2 "2

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 corresponding surface reaction rate can be given by C 28C 7 r8 = ' 8 C A 8C 7 C 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 detachment / ' ;2C2.8 5

.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

!:$.*:&

C T 8 rA= = ' T "T C 7 C T

!:$.**&

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 2 "2C 7 r8 = ' 8 " C " C H T T 7 * C 8

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

which can be written in lineari ed form as follows@

"H * "T r8 = : + C T "T + C 2 "2 'C T = C2 : : "T + "2 + ' 'C T 'C T

!:$.*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