9/12/2017

THE DETERMINATION of THE RATE EQUATION IS USUALLY A TWO STEP

PROCEDURE :
1. THE CONCENTRATION DEPENDENCY IS FOUND AT FIXED TEMPERATURE
2. THE TEMPERATURE DEPENDENCE OF THE RATE CONSTANTS

INTERPRETATION of DATA EMPIRICAL INFORMATION IS OBTAINED BY ……………., USUALLY OPERATED

from REACTOR BATCH …………………………… AND CONSTANT ………………

I TWO PROCEDURES FOR ANALYZING KINETIC DATA :

1. MOLE BALANCE INTO BATCH REACTOR :

I. INTEGRAL METHODE
dC A ……… (1)
1 A MOLE BALANCE (BATCH REACTOR) IS CONTRUCTED rA  OR
2. THE EQUATION OF REACTION RATE IS ESTIMATED dt
3. THE STOICHIOMETRIC OF MATERIALS WHICH INVOLVED THE
REACTION IS EVALUATED
4. COMBINED, INTEGRATED, ARRANGED TO A STRAIGHT LINE
EQUATION - rA = f (k, C) ……… (2)
5. PLOT BETWEEN CONCENTRATION/ CONVERSITION VERSUS
TIME
6. IF A PLOT YIELDS A STRAIGHT LINE, THE ASSUMPTION OF THE
REACTION RATE IS TRUE. IF WRONG, REPEAT STEP 2 UNTIL 5 2. FROM EQ.(1) AND (2) :

dC A INTEGRATED WILL BE
  kdt OBTAINED
f (C )
CA t
dC A
 
C AO
f (C A )
 k  dt  kt
0
……………… (3)

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3. CONCENTRATION FUNCTION IS PROPORTIONAL TO TIME. PLOT AS IRREVERSIBLE UNIMOLECULAR-TYPE FIRST –ORDER REACTIONS
THAT OF FIG 1 YIELDS A STRAIGHT LINE OF SLOPE k

A → PRODUK ……………….. (4a)

FIT WITH EQ.(3) Mole balance of A into reactor batch:

…………………… (4b)
REJECTED, NOT FIT
WITH EQ..3

Rate reaction of A is ………… (4c)

EQ. (4c) INSERTED TO EQ. (4b) THEN INTEGRATED : :

CA t
dC A
  k  dt
FIG. 1. TEST of A RATE EQUATION BY THE INTEGRAL ANALYSIS
 → …………….. (5)
C AO
CA 0

IF EQ (4b) IS DEFINED USING CONVERSIONS :

dX A
 k (1  X A )
dt
REARRANGING AND INTEGRATING GIVES: EQ.(5) OR
EQ.(6)

 ln( 1  X A )  kt ….. (6)

PLOT ln (1-XA ) OR ln (CA /CAO ) VERSUS t ,

OBTAINED A STRAIGHT LINE AS FIG. (2) FIG 2. TEST FOR THE FIRST-ORDER REACTION, EQ (6)

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II. IRREVERSIBLE BIMOLECULAR-TYPE SECOND-ORDER REACTIONS LETTING M = CBO /CAO , WILL BE OBTAINED:

……………… (7d)
A + B → PRODUCTS

IF THE REACTION IS ELEMENTER AND A IS LIMITING IF EQ. (7d) REARRANGED AND INTEGRATED:
REANCTANT :
…………. (7)

EQ. (7) → EQ. (4b) GIVES :

1 (M  X A )
ln  C AO kt OR
( M  1) ( M (1  X A ))
……………… (7b)

(M  X A )
IN TERM OF CONVERSION : ln  C AO ( M  1) kt …………… (8)
CA = CAO (1-XA ) DAN ( M (1  X A ))

………… (7c) M≠ 1

PLOT FOR EQ. (8) : II a. SECOND ORDER REACTION

2 A → PRODUK
FROM MASS BALANCE IN BATCH REAKTOR :

RATE of
REACTION

COMBINATION :

CAO (M-1)k

ARRANGED AND INTEGRATED:

dC AO (1  X A ) 2
  kC AO (1  X A ) 2
FIG 3. TEST FOR THE SECOND-ORDER REACTION dt
XA t
dX A dX A
 (1  X A ) 2 0
2
C AO  kC AO (1  X A ) 2   kC AO dt
dt 0

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III. ZERO-ORDER REACTIONS (IRREVERSIBLE REACTION)

…………….. (9) EQUATION OF REACTION RATE OF A : …….. (10)

EQUATION (9) INSERT TO EQ. (4b) :

…………….. (11)
PERS.9

Pers.9
IF EQ. (10) IS INTEGRATED

CA t


C AO
 dC A   k dt
0
ATAU :

FIG 3a . TEST FOR SECOND ORDER

C A  C AO  kt ………………. (13)

IV. n ORDER REACTION (IRREVERSIBLE)

REACTIN RATE OF A IS SUGGESTED AS:

IF INTEGRATED :

………. (14)

n estimated , THEN EQ. 14 IS solved :

FIG. 4. TEST FOR A ZERO-ORDER REACTION

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IV a. “ THE HALF-LIFE” , t1/2 EXAMPLE :

t1/2 : TIME NEEDED FOR CONCENTRATION OF REACTANT
TO DROP TO ONE-HALF THE ORIGINAL VALUE.

OR CA = ½ CAO EQUATION (14) BECOME :

ANSWER :

MASS BALANCE OF BATCH REACTOR (EQ. 1) :

RATE OF REACTION IS ASSUMED FIRST ORDER :

COMBINED AND SOLVED ( EQ. 5):

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Solved by FRACTIONAL LIFE METHOD

1. Mass (mole) balance for batch reactor :
(METHOD t0,8 )
AT t0,8 CONCENTRATION OF CA = 0,8 CA0
2. Guess second order rte of reaction
3. Create a new table :

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CALCULATE OF k

FROM TABLE 4 ,
AT CAO = 10 Mol/l OBTAINED t0,8 = 18,5 SEC, THEN

INSERTED TO EQ. 16 :

THE RATE REACTION EQUATION IS: