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KINETIC MODELS FOR NONELEMENTARY REACTIONS THE REACTION SCHEMES CAN BE OF TWO TYPES :

FOR EXAMPLE , A SINGLE REACTION : 1. NON CHAIN REACTION

A2 + B2 2 AB ………….. (1) INTERMEDIATE IS FORMED , AND REACTS TO GIVE PRODUCT.

REACTANS → (INTERMEDIATES)
THE ARGUMENT ARE OCCURRED UNOBSERVED INTERMEDIATE SUBSTANCES
AND POSTULATE A SERIES OF ELEMENTARY STEPS TO EXPLAIN THE KINETICS,
SUCH AS : 2. CHAIN REACTIONS
a. A FIRST REACTION, CALLED CHAIN INITIATION, IS
A2 2 A INTERMEDIATE FORMS
A +B2 AB + B
b. THEN CHAIN PROPAGATION STEP, INTERMEDIATE COMBINES
A + B AB WITH REACTANT TO FORM PRODUCT AND MORE INTERMEDIATE

(INTERMEDIATE) + REACTAN T → (INTERMEDIATE) + PRODUCT

THE TYPES OF INTERMEDIATES MAY AS :
c. FINALLY, TERMINATION STEP, THE INTERMEDIATE IS
DESTROYED

TESTING KINETIC MODELS: Equation (1) and (2) are breakdown to :

1. Propose more than one mechanism k1
2. Consistency between the propose mechanism with kinetic data from 2A A2 * …………… (3)
experimental. k2
A2 * 2A …………… (4)
k3
Example : Search for the reaction mechanism A2 * +B A2 B …………… (5)
k4
The irreversible reaction has a stoichiometric equation A2 B A2 + B
* …………… (6)
2 A + B → A2 B
From experiments obtained the rate of formation A2 B as FROM EQUATION (5, AND 6)
2
0,72C A CB 0,72[ A]2 [ B]
rA2 B   ………… (7)
1  2C A 1  2[ A]
A2* not detected and hence should be stated in another concentration as
Mechanism is proposed as follows : [A], [B], ATAU [A2 B].

…….(8)

[A2 ] SMALL
* rA *  0
2

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EQUATION (8) BEING : IF k4 <<<< , equation (10) become :

(k1k3 / 2k 2 )[ A]2 [ B ]
rA2 B  ……….. (12)
1  (k3 / k 2 )[ B ]
* 1 / 2k1[ A]2  k 4 [ A2 B] …………. (9)
[ A2 ] 
k 2  k3[ B]
MODEL 2
EQUATION (9) EQUATION (8)
k1
A + B ABӿ ……….. (13)
k2
…………. (10)
k3
ABӿ + A A2 B …………. (14)
k4

IF k2 <<< , equation(10) become :

…………… (15)
rA2 B  1 / 2k1[ A]2 …………. (11)
ELIMINATE [AB* ] :

FROM WHICH : CONCLUSION :

[ AB ] 
* …………….. (16) MODEL 1 IS REJECTED AND MODEL 2 IS ACCEPTED
k1
A + B AB*
k2
REPLACING Eq. (16) in Eq. (15), obtained :

rA2 B  …………… (17) k3

AB* +A A2 B
If k4 <<<<< eq.(17) become :

rA2 B  ………… (18)

Comparing Eq. (18) and Eq. from experiment :

2
0,72C A CB 0,72[ A]2 [ B ] THE SAME FORM
rA2 B  
1  2C A 1  2[ A]

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SISTEM BATCH : rA V = dNA /dt …………. (2)

A + b/a B → c/a C + d/a D
STOICHIOMETRIC TABLE FOR A BATCH REACTOR
A, selected as limiting reactant -------------------------------------------------------------------------------------------
SPESIES INITIALLY CHANGE REMAINING
(MOL) (MOL) (MOL)
MOLE BALANCE EQUATION FOR REACTOR -------------------------------------------------------------------------------------------
BATCH :

THE GENERAL MOLE BALANCE :

RATE OF GENERATION
  RATE OF ACCUMULATION 
RATE of FLOW of A  RATE OF FLOW OF A   OF A BY CHEMICAL   
INTO THE SYSTEM    OUT OF THE SYSTEM    REACTION  OF A
  
   
  WITHIN THE SYSTEM 
(d/a + c/a –b/a -1 ) = δ
 WITHIN THE SYSTEM 

TOTAL NUMBER OF MOLES AFTER REACTION P1

… (1) : NT = NTO +δ NAO X

STOICHIOMETRIC TABLE IS FORMED TO CONCENTRATION :

FOR THE VOLUME CONSTANT SYSTEM : V = VO

EQUATION (3) AND (4) BECOME :

………… (3)

……….. (5)

………… (4)

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Slide 10

P1 Presario, 7/29/2017
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FLOW SYSTEM

v STOICHIOMETRIC TABEL FOR A FLOW SYSTEM

vo A + b/a B → c/a C +d/a D ------------------------------------------------------------------------------------------------------------------------
FAO FA SPESIES Feed Rate to Change within Effluent Rate from

FBO FB Reactor
(MOL/WAKTU)
Reactor
(MOL/WAKTU)
Reactor
(MOL/WAKTU)
FCO FC ------------------------------------------------------------------------------------------------------------------------------------

FDo FD
FA moL / waktu moL
CA   
V v L / waktu L

FOR LIQUIDS, VOLUME CHANGE WITH REACTION NEGLIGIBLE

v = vo

VOLUME CHANCE WITH REACTION

FROM STOCHIOMETRIC TABEL : NT =NTO +δ NAO X

IF DIVIDED BY NTO YIELDS :
FOR IDEAL GAS :
………….. (9)
……………………. (6)
→ VALID AT ANY POINT IN THE SYSTEM AT ANY TIME, t
WHERE : yAO = mole fraction A initially present

d c b …………(10)
AT REACTION IS INITIATED: …..(7)    1
a a a
IF EQUATION (6) DIVIDED BY(7) AND REARRANGING YIELDS :
yAO δ = ε ………… (11)
P  T  N  ………….. (8)
V  VO  O   T 
 P  TO  N TO 
change in total number of moles for complete conversion
 
total number of moles fed to the reactor

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EQUATION (8) BECOME :

…………………… ( )

FOR FLOW SYSTEM :

P  T …………………… ( )
v  vO  O  1  X 
 P  TO