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Metode analisis kecepatan

4 metode
• 1. Integral
• 2. Differensial
• 3. Laju awal
• 4. Waktu paruh
Reaksi Orde Satu

• Pada reaksi orde satu, kecepatan reaksi berbanding
lurus dengan konsentrasi reaktan.
• Persamaan laju reaksi orde satu dinyatakan sebagai :

- = k
1
[A]

- = k
1
dt

ln = k
1
(t – t
0
)

Bila t = 0  A = A
0

ln [A] = ln [A
0
] - k
1
t
[A] = [A0] e
-k
1
t
dt
dA
] [
] 0 [
A
A
] [ A
dA
Tetapan laju (k
1
) dapat dihitung dari grafik ln [A]
terhadap t, dengan –k
1
sebagai gradiennya.

ln [A]
ln [A]
0

gradien = -k
1

t
Grafik ln [A] terhadap t untuk reaksi orde satu
Waktu paruh (t
1/2
) adalah waktu yang
dibutuhkan agar konsentrasi reaktan
hanya tinggal setengahnya. Pada reaksi
orde satu, waktu paruh dinyatakan
sebagai
k
1
= ln

k
1
=
t1/2
1
2 / 1
1
2 / 1
693 , 0
t
. Reaksi Orde Dua
• Persamaan laju reaksi untuk orde dua
dinyatakan sebagai :
- = k
2
[A]
2

- = k
2
t

- = k
2
(t – t
0
)
dt
dA
2 ] [A
dA
] [
1
A ] 0 [
1
A
Tetapan laju (k
2
) dapat dihitung dari grafik 1/A terhadap
t dengan k
2
sebagai gradiennya.










ln 1/[A]
ln 1/[A]
0

gradien = -k
2

t
Grafik ln 1/[A] terhadap t untuk reaksi orde dua
Waktu paruh untuk reaksi orde dua dinyatakan sebagai
t
1/2
=
] 0 [ 2
1
A k
Menentukan Orde Reaksi dari
Persamaan Laju Integral
| | | |
| | | |
0
0
1 1
ln ln
A
kt
A
A kt A
t
t
+ = + ÷ =
Waktu Paruh Reaksi
Reaction Order Using the
Integrated Rate Equations
Order in [A] Rate Law Integrated Form,
y = mx + b
Straight Line
Plot
Half-Life t
1/2

zeroth
order
(n = 0)
rate = k [A]
o
= k [A]
t
= - k t +[A]
o
[A]
t
vs. t
(slope = - k)
first
order
(n = 1)
rate = k [A]
1
ln[A]
t
= - k t +
ln[A]
o

ln[A]
t
vs. t
(slope = - k)
second
order
(n = 2)
rate = k [A]
2

vs. t
(slope = k)
1
[ A]
t
= k t +
1
[A]
0

1
[A]
t
t
1/ 2
=
[A]
0
2k
t
1/ 2
=
ln2
k
=
0.693
k
t
1/ 2
=
1
k[A]
0
These types of plots are usually used to determine the values k for runs at
various temperatures and then used to determine the activation energy.
• Zero Order First Order Second Order

















Differential Method






• Taking the natural log of


• The reaction order can be found from a ln-
ln plot of:

time (s) 0 t
1
t
2
t
3

concentration (mol/dm3) C
Ao
C
A1
C
A2
C
A3

Three Ways to Determine (-dCA/dt) from Concentration-Time Data (Graphical,
Polynomial, Finite Difference, Non-Linear Least Squares Analysis)



However, we are usually given concentration as a function of time from
batch reactor experiments.


Graphical

This method accentuates measurement error!
Polynomial (using Polymath)

• C
A
= a
o
+ a
1
t + a
2
t
2
+ a
3
t
3
+a
4
t
4


Finite Difference

METHODA LAJU AWAL
 Disini, diukur r
o
untuk beberapa run percobaan.
 Variasi konsentrasi awal dari satu reaktan pada waktu
tertentu
Misal diukur r
Ao
dua konsentrasi awal dari A , yaitu
C
Ao,1
dan C
Ao,2
dengan C
Bo
, C
Co
, - - - dibuat tetap.
 Karena hanya C
ao
yang berubah sedangkan yang
lainnya dijaga tetap, misal untuk persamaan laju reaksi :
- r
A
= k C
A
a
C
B
b
C
C
c
- - - ,
laju reaksi untuk run 1 dan 2 :
r
Ao,2
C
Ao,2
--------- = ---------
r
Ao,1
C
Ao,1
a
. . . (121)
 maka data a dapat ditentukan..
 Laju reaksi awal - r
Ao
dapat dicari dari data
differensial pada waktu = 0
 Orde reaksi b , c , - - - dapat dicari dengan acara
yang sama.

Contoh 1. The initial-rate method
Kelarutan dolumite, calcium magnesium carbonate dalam
HCl adalah
4HCl + CaMg(CO
3
)
2
÷÷ Mg
+2
+ Ca
+2
+ 4Cl
-
+ 2 CO
3
+ 2H
2
O
Tentukan orde reaksi HCl dari data seperti pada Fig.1
Solution
- r
A
= k C
A
a
C
B
b
- r
Ao
= k C
Ao
a
C
bo
b


 C
Bo,1
= C
Bo,2
and C
Ao,1
= C
Ao,2
- r
Ao,2
C
Ao,2
----------- = ---------
- r
Ao,1
C
Ao
,
1

a
Run 1 Run 2





4N HCl





1 N HCl
4.000
3.999
3.998
3.997
3.996
0 2 4 6 8
t (min)

C
H
C
l

1.0000
0.9990
0.9980
0.9970
0.9960
t (min)
0 2 4 6 8
C
H
C
l

Figure 1
- dC
A
3.9982 - 4.000
-r
AO,2
= ------- = -------------------------- = 3.6 x 10
–4
mole/lt min
dt 5 - 0

- dC
A
0.9987 - 1.0000
-r
Ao
,
1
= -------- = ---------------------------- = 2.2 x 10
–4
mole/lt.min
dt 6 - 0
Jadi :
- r
Ao,2
C
Ao,2
----------- = ----------
- r
AO,1
C
Ao,1

a
3.6 x 10
–4
4
------------- = ------
2,2 x 10
– 4
1
a
a = 0.44.
Orde reaksi b dicari dengan cara yang sama dimana hanya
(C
Bo
) yang berubah
• EXAMPLE: Given the following experimental kinetic data, determine the kinetic
rate expression and overall order of reaction.
• 2HgCl
2
+ C
2
O
4
2-
------ Hg
2
Cl
2
+ 2CO
2
+ 2Cl
-










• Our tentative rate expression for this reaction is:
rate = k[HgCl
2
]
x
[C
2
O
4
2-
]
y

• We need to determine what the exponents (orders) x and y are on the reactant
concentrations. Then we can solve for the rate constant k.
• Step #1: find two experiments where the concentration of one of the reactants
stays the same. Since the rate constant k is a constant and the concentration
of one of the components is not changing (also a constant for this
comparison), we only have to worry about the one reactant that is changing.
Exp # [HgCl
2
] [C
2
O
4
2-
] Initial Rate
1 0.10 M 0.15 M 2 x 10
-5

2 0.10 M 0.30 M 8 x 10
-5

3 0.05 M 0.30 M 4 x 10
-5

We can then set up the following proportionality:

Rate(exp #2)
8 x 10
-5
2 x 10
-5
Rate(exp #1)
=
=
=
=
[ ]
exp#2
A
y
[ ]
exp#2
A
[ ]
exp#1
A
y
[ ]
exp#1
A
y
y
y
0.30
0.15
4
(2)
If you can’t solve this by inspection, then
take the of each side of the equation: log
log(4) = log(2) y
Rearrange and solve for : y
y =
log(4) 0.602
log(2) 0.301
= = 2
Step #2: Repeat for the other reactant
concentration terms in the rate equation:

Rate(exp #2)
8 x 10
-5
4 x 10
-5
Rate(exp #3)
=
=
=
[ ]
exp#2
A
[ ]
exp#3
A
x
x
x
0.10
0.05
2
(2) x = 1
Now that we have solved for the orders of the kinetic
rate expression, we can write out the rate equation:
rate = k[HgCl
2
][C
2
O
4
2-
]
2

• The overall order of the rate expression is the sum of
the individual orders (x + y): 1 + 2 = 3. So this is
called a third order rxn or rate law.
• Note that the orders DO NOT correspond to
the coefficients on the chemical equation.
Many times they do, but just as many times
they won’t. There is NO FORMAL
CONNECTION!!
Step # 3: Calculate the rate constant (if asked for). We
now just plug in the experimental data from any one of
the experiments and rearrange and solve for k, the rate
constant. For this example we will use the data from
experiment # 1.

rate
2
= [HgCl ] [C O
-
]
2 2 4
2
k
[HgCl ] [C O
-
]
2 2 4
2 2
k =
k =
k =
rate
2 10
x
-5
2 10
x
-5
2.25 10
x
-3
k = 8.88 10
x
-3
(0.10 M) (0.15 M)
2
M sec
-1
M sec
-1
M
3
M sec
-2 -1
• Consider a reaction A + B + C-> Products (this, too, is not an
elementary reaction). Several initial conditions of this reaction are
investigated and the following data are obtained:


Run
#
[A]
0
[B]
0
[C]
0
v
0

1 0.151 M 0.213 M 0.398 M 0.480 M/s
2 0.251 M 0.105 M 0.325 M 0.356 M/s
3 0.151 M 0.213 M 0.525 M 1.102 M/s
4 0.151 M 0.250 M 0.480 M 0.988 M/s
rate = k [A]
a
[B]
b
[C]
c

The ratio of the initial rates of runs 1 and 3 is then:


• Note that we have chosen this ratio so that many terms on the right
hand side cancel, i.e. k and the concentrations of species A and B.
The ratio reduces to:


• Note that none of the numbers in this equation have any
units anymore because we have divided them out in a
dimensionless ratio. Now, how to solve for c? Take the
natural log (i.e. ln) of both sides of the equation

• Atau


• To continue, we pick another pair of runs that have a change in the
initial concetration of C and just one other reactant. Let us choose
the runs 1 and 4. The ratio of the initial rates of these runs is:



• Note that everthing cancels, is known, or is the order b. So:


• We can determine b as before by taking the ln of both sides of this
equation:


• and b = 1.00. The reaction is First Order in B!
Now that we know the order of Reactants A and B, we can use
another pair of experimental runs to determine the remaining
unknown order. We must use a pair of runs where the initial
concentration of A changes, so we pick runs 1 and 2. As before, the
ratio of initial rates is


• The rate constant cancels as before and we can solve for a:


• and, as usual, take the ln of both sides:


which results in a = 2.00 and the reaction is Second Order in A.


The rate constant for the reaction may now be evaluated from any of
the experimental runs:


Atau
k = 1.57 x 10
3
l
5
/ mol
5
.s




Problem:
Consider the following reaction and kinetic data.
What is the kinetic rate expression?
• Ni(CO)
4
+ CNCH
3
Ni(CO)
3
(CNCH
3
) + CO


Exp # [Ni(CO)
4
] [CNCH
3
] Initial Rate
(Msec
-1
)
1 0.04 0.06 0.2 x 10
-5

2 0.04 0.12 0.2 x 10
-5

3 0.08 0.06 0.4 x 10
-5

4 0.08 0.12 0.4 x 10
-5

Problem:
Consider the following reaction and kinetic data. What
is the rate constant?
• CO(g) + H
2
O(g) CO
2
(g) + H
2
(g)

Exp # [CO] [H2O] Initial Rate (Msec
-1
)
1 1.5 1.5 0,2
2 1.5 4.5 0,6
3 3.0 4.5 1,2
4 1.5 0.75 0,1
5 3.0 3.0 0,8
problem
Dari percobaan reaksi A + B  AB, diperoleh data sebagai berikut
Perc [A] M [B] M V M/s
1
2
3
4
1,3.10
-2
6,5.10
-3
3,9.10
-2
1,3.10
-2
2,1.10
-2
1,05.10
-2
4,2.10
-2
1,05.10
-2
1,4.10
-1
3,5.10
-2
8,4.10
-1
7.10
-2
Tentukan
A. Orde reaksi untuk A dan B
B. Persamaan laju reaksi
C. Harga tetapan laju reaksi
D. Laju reaksi jika konsentrasi A 0,026 M dan konsentrasi B
0,021 M
1
2
3
4
5
The following data were obtained for
the reaction A + B + C products:

Experi-
ment
[A]
0
[B]
0
[C]
0

Initial rate, v
0
(mol L
-1
s
-1
)
1 1.25 x 10-3 M 1.25 x 10-3 M 1.25 x 10-3 M 0.0087
2 2.50 x 10-3 M 1.25 x 10-3 M 1.25 x 10-3 M 0.0174
3 1.25 x 10-3 M 3.02 x 10-3 M 1.25 x 10-3 M 0.0508
4 1.25 x 10-3 M 3.02 x 10-3 M 3.75 x 10-3 M 0.457
5 3.01 x 10-3 M 1.00 x 10-3 M 1.15 x 10-3 M ?
(a) Write the rate law for the reaction.
(b) What is the overall order of the reaction?
(c) Determine the value of the rate constant.
[Hint: Use your rate law from (a) and appropriate data.]
(d) Use the data to predict the reaction rate for experiment 5.
Penentuan Hukum Laju Cara Waktu paruh
[ ]
n
dA
k A
dt

Untuk reaksi orde n:
0
[ ]
[ ] 0
[ ] [ ]
A t
n n
A
A d A k dt =÷
} }
1
0
[ ] [ ]
1
n
A A
k t
n
÷ +
÷
=
÷ +
1
0
(1 )[ ]
n
x n A
÷
÷
1
0
0
[ ]
1 [ ] ( 1) . 1
[ ]
n
A
A n kt ut n
A
÷
| |
= + ÷ =
|
\ .
Untuk [A] = ½ [A]
0
dan t = t
1/2

1
1/ 2
1
0
2 1
. 1
( 1)[ ]
n
n
t ut n
n A k
÷
÷
÷
= =
÷

Persamaan laju reaksi :
- 1 dN
A
mole A

- r
A
= ------ -------- ----------------
V dt (volume)(waktu)

Bentuk lain :
- 1 dN
A
mole A

- r
A
= ------ -------- ------------------------------------------
S dt (luas permukaan solid)(waktu)
- 1 dN
A
mole A

- r
A
= ------ -------- -----------------------------
W dt (berat katalis)(waktu)

Reaktor batch (phase gas) :
volume reaktor konstan tetapi terjadi perubahan
jumlah mole selama reaksi ( tekanan total t akan
berubah dengan perubahan waktu ) , atau
aA + bB r R + s S . . . (1)
A n = ( r + s ) - ( a + b )
Untuk reaktan A : p
A
= C
A
RT = p
Ao
+ ------- ( t
o
- t)

a
A n
Untuk produk R : p
R
= C
R
RT = p
RO
- ------- ( t
o
- t)
. . . (2)
r
An
Reaktor batch :
Phase gas : konstan tekanan maupun temperatur ,
tetapi terjadi perubahan jumlah volume atau densiti
selama reaksi yaitu :
V = Vo (1 + c
A
.X
A
) . . . (3)
dimana c
A
. Adalah fraksi perubahan volume, atau


V
A habis bereaksi
- V
A mula-2
V
XA=1
- V
XA=0
c
A
. = -------------------------------- = ----------------------
V
A mula-2
V
XA=0
7
- Untuk sistem volume & densiti konstan :
dV = 0 dan N
A
= C
A
.V

- r
A
= ---- --------- = ---- -----------------

- 1 d(C
A
.V) -1 V dC
A
+ C
A
dV
V dt V dt
= 0
or
- r
A
= ----- ------- = ---------
-1 dN
A
- dC
A
V dt dt
12
KONSENTRASI dan TEKANAN PARSIAL
Seperti pada Pers diatas:
- r
A
= - (1/V)(dN
A
/dt) = k
C
C
A
a
C
B
b
. . . . . (4)
Hubungan antara konsentrasi dengan tekanan parsial
dari hukum gas ideal :
p
A
= C
A
RT
Persamaan laju reaksi menjadi :
- r
A
= - ----- ------- = k
C
C
A
a
C
B
b


17
1 dN
A
V dt

- r
A
= ------------- = k
C
( ------- )
(a+b)
p
A
a
p
B
b


- r
A
* =

-------- = k
C
( RT )
1 - (a+b)
p
A
a
p
B
b

= k
P
p
A
a
p
B
b
(unit tekanan) / (unit waktu)
. . . (5)



d(p
A
/RT) 1
dt RT
dp
A
dt
18
- r
A
= -------- = k
C
p
A
a
p
B
b
mol/unit volume.wkt

dapat dinyatakan sebagai :

- dC
A
dt
Untuk volume konstan :



19
Dimana laju reaksi spesifik atau konstanta laju
reaksi adalah
k
P
= k
C
(RT)
1 - n ;
n = a + b

Untuk reaksi fasa gas komposisi dalam persamaan
laju reaksi umumnya dinyatakan dalam bentuk
tekanan parsial dari komponen yang bereaksi.
Pada berbagai situasi biasanya lebih baik bila
konsentrasi diubah ke tekanan parsial sehingga lebih
mudah dalam evaluasinya.

. . . (16)
. . . (17)
- r
A
= k
C
. C
A
a
C
B
b
- r
A
= k
P
p
A
a
p
B
b



(mol/lt)
1-n
/jam
mol/lit.ja
m
(mol/lt)
n

mol/lit.atm
n
. jam

mol/lit. jam (atm)
n

k
P
= k
C
(RT)
–n
mol/lit.atm
n
.jam
Contoh 1. Mengubah bentuk tekanan ke konsentrasi
Pada 610
o
K dan 1 atm, reaksi bolak balik elementer diketahui
sebagai berikut :
2 A B,
- r
A
= k
1
p
A
2
– k
2
*
p
B
mol/lit.jam ( k
2
*selerusnya ditulis k
2
)

Ubah laju reaksi ini ke unit konsentrasi & tekanan
a. - r
A


= k
1
C
A
2
– k
2
C
B
mol/lit.jam
b. - r
A
* = k
1
”C
A
2
– k
2
” C
B
atm/jam
Data diketahui : 1. k
1
; 2. K
P

3. T ; 4. t
k
1
= 10
-3
mol/lt.atm
2
jam
Kp = 0,5 atm
-1


1
2



Solution :
a.) diketahui - r
A
= k
1
p
A
2
– k
2
p
B
(mole/lit.jam)
diingini bentuk - r
A
= k
1
* C
A
2
– k
2
* C
B
(mole/liter.jam)
jadi disini bentuk dari – r
A
tetap sebagai – dC
A
/dt mole/liter.jam
atau yang akan diubah hanya bentuk p
A
dan p
B
ke C
A
dan C
B
Diketahui : p
A
= C
A
.RT
mol mol mol
- r
A
= (10
-3
------------- )( p
A
2
atm
2
) – ( k
2
--------------)(p
B
atm) ---------
lit.atm
2
.jam lit.atm.jam lit.jam



mole
k
1
p
A
2
= (10
-3
-------------- ) { ( C
A
RT)
2
}

(atm)
2
lit atm
2
jam

mole liter.atm
C
A
.RT = ----------- ----------------
o
K = atm
liter mole.
o
K
Jadi :
k
1
.p
A
2
= ( 10
-3
mole/lt.atm
2.
jam

) [ C
A
2
(

mole/lt)
2
] [ (0,082 )(610) ]
2

(liter.atm/mole)
2

= (10
–3
)(0,082)
2
(610)
2
C
A
2


mole/liter.jam

= 2,5 C
A
2
mole/liter.jam

k
2
.p
B
= ( 2 x 10
-3
------------ ) ( p
B
atm )

k
2
p
B
= ( 2 x 10
–3
)( C
B
RT)
= ( 2 x 10
–3
)(RT) C
B

= k
2
” C
B

k
2
” = (2 x 10
–3
------------ )(0,082 ----------- )( 610 K)
= 0,1 jam
-1


mol
lit atm jam
lit.atm
mol.
o
K
mol
lit.atm.jam


25
K
P
= 0,05 atm
–1
=

----- or k
2
= ----- = -------------------------
10
-3
mol/lit.atm
2
.jam
0,5 atm
-1

k
1
k
1

k
2
K
P
Persamaan yang diingini menjadi :
- r
A


= 2,5 C
A
2
– 0,1C
B
mol/lt.jam
b. Diingini : - r
A
*
dalam atm/jam
dari :
dC
A
- r
A
= ------- = k
1
.p
A
2
- k
2
p
B
mol/lit.jam
dt

dC
A
1 dp
A
- r
A
= ------- = ----- ---------

(

mol/lit.jam)
dt RT dt


- r
A
= -------- = ----- --------- = k
1
.p
A
2
– k
2
.p
B
mole/lit.jam

- r
A
* = ------- = k
1
(RT) p
A
2
- k
2
(RT) p
B
atm/jam

- dC
A
dt
-1 d p
A
RT dt
- dP
A
dt
k
1
RTp
A
2
= (10
-3
mol/lit.atm
2
.jam)(0,082 lit.atm/mol. K) (610 K) p
A
2
atm
2


= 0,05 . p
A
2
atm/jam

k
2
RT p
B
= (2 x 10
–3
mol/lit.atm.jam )(0,082 lit.atm/mol. K)(610 K) p
B


= 10
–1
p
B
atm/jam
Persamaan laju reaksi menjadi :


- r
A
* = 0,05 p
A
2
- 0,1 p
B
atm/jam



24
Contoh 2. Mengubah tekanan ke konsentrasi
Reaksi dengan persamaan stoikiometeri : A ÷÷ R (aq)
dengan persamaan laju reaksi : - r
A
= 0,5 C
A
2
mol/lit.det
terjadi pada 100
o
C & 1 atm.
Ubah bentuk ini ke bentuk unit konsentrasi dan tekanan
a). - r
A
* = k
P
p
A
2
mol/lit.det
b). - r
A
” = k
P
p
A
2
atm/ det
Solution :
a), - r
A
= - r
A
* mol/lit.det or 0,5 C
A
2
= k
P
p
A
2
mol/lit.det
(0,5)(p
A
/RT)
2
= k
P
p
A
2

mol/lit.det
{ 0,5 / (RT)
2
} p
A
2
= k
P
p
A
2
mol/lit.det
- r
A
= (0,5)/{(0,082 lit.atm/mol. K)(373 K)}
2
p
A
2
atm
2

-r
A
* = 5x10
- 4
p
A
2
= k
P
p
A
2

k
P
= 5 x 10
-4
mol/lit.atm
2
det
25
b). - r
A
’ = -dp
A
/dt atm/det
- r
A
= - dC
A
/dt = 0,5 C
A
2

- r
A
= - d(p
A
/RT)/dt = 0,5 (p
A
/RT)
2

- r
A
= - (RT)
–1
dp
A
/dt = 0,5 (RT)
–2
p
A
2

- r
A
’ = - dp
A
/dt = { 0,5 (RT)
1 – 2
} p
A
2
atm/det
- r
A
’ = - dp
A
/dt = [0,5/{(0,082)(373)}
–1
] p
A
2
atm/det
- r
A
’ = - dp
A
/dt = 0,016 p
A
2
atm/det
where k
P
’ = 0,016 (atm.det)
-1


89
Contoh 10 : Order of reaction

Hinshelwood dan Askey mempelajari reaksi phase gas
dari dekomposisi dimethylether dengan mengukur
kenaikan tekanan :
Reaksi
(CH3)2O ÷÷ CH4 + H2 + CO
Data diperoleh pada 504
o
C dan tekanan awal ether 312
mm, adalah :
Kenaikan tekanan,mm : 96 176 250 467 619
Waktu, sec : 390 777 1197 3155 ·
Hitunglah orde reaksi dan konstanta laju reaksi k.
Solution :
• Reaksi : A ÷÷ R + S + T
• Assumsi : reaksi orde satu
90
- dC
A
/dt = k.C
A
atau - dp
A
/dt = k.(RT)
1-1
p
A

- ln (p
A
/p
AO
) = k.t
a
Dari Eq. (2) p
A
= p
Ao
- ----- ( t - t
O
)
An

reactant A murni atau p
AO
= t
O

Jadi
a
p
A
= t
O
- ------ ( t - t
O
)
An

1
p
A
= 312 - ---- ( At )
3-1

p
A
= 312 – ½ ( A t )
Pada t = 390 sec, p
A
= 312 – ½ (96) = 264 mm
Begitu juga untuk data yang lain :

91
Diperoleh At pada berbagai t.
t At p
A
p
A
/p
Ao
- ln (p
A
/p
Ao
)


390 96 264 0.843
777 176 226 0.724
1197 250 187 0.599
3155 467 78,5 0.251

Apabila di plot - ln (p
A
/p
AO
) terhadap waktu (t),
menunjukkan garis lurus maka reaksi mengikuti reaksi orde
satu
slope >> k = sec
-1


92
k1
k2
Contoh 11. Reaksi bolak balik
Nitrogen dan oxygen bereaksi membentuk nitrous oxide pada
2700 K pada batch reaktor volume tetap ( 0.4 dm
3
) pada
tekanan 20 atm. Feed terdiri dari 77% N
2
, 15% O
2
, dab 8% gas,
lain yang dapat dianggap sebagai inerts. Pada temperatur ini
konstanta kesetimbangan Ke adalah 0.01.
Apabila konversi 80% dari konversi kesetimbangan terjadi
pada 151 µdet, maka tentukan konstanta laju reaksi ke kanan.
Solution
Reaksi : N
2
+ O
2
2 NO
atau A + B 2 R
Keadaan setimbang :
( - r
A
)e = 0 = k
1
C
A
C
B
– ½ k
2
C
R
2
93
- r
Ae
= 0 = k
1
C
A
C
B
– k
2
’ C
R
2
. . . (i)
C
R

0 = k
1
C
A
C
B
- ------ . . . (ii)

Ke

2
Batch reaktor volume tetap : c
A
= 0, and
C
A
= C
Ao
(1 – X
A
) . . . (iii)
C
B
= C
AO
( M – X
A
) . . . (iv)
C
R
= C
Ro
+ 2C
Ao
X
A
= 2C
Ao
+ X
A
. . . (v)
Dari Eq (ii) dan Eq(v) diperoleh
4X
e
2
= K
e
(1 – X
e
)(M – X
e
) . . . (vi)
4
----- - 1 X
e
2
+ (1 + M) X
e
- M = 0 . . . (vii)
Ke

M = C
Bo
/C
Ao
= 0.15/0.77 = 0.195
Substitusi K
e
= 0.01 dan M dalam Eq (vii), maka :
94
399 X
e
2
+ 1.195 X
e
- 0.195 = 0
Atau X
e
= 0.02
Untuk 80% dari konversi kesetimbangan :
X
A
= (0,8)(0.02 ) = 0.016
Laju reaksi :
- r
A
= -------- = k
1
C
A
C
B
– k
2
’ C
R
2


C
Ao
dX
A
------------- = k
1
C
Ao
2
(1-X
A
)(M-X
A
) – (k
1
/Ke)(C
Ao
X
A
)
2

dt
1 dX
A
t = -------- ------------------------------------


k
1
C
Ao
(1 – X
A
)(M – X
A
) – 4X
2
/Ke

y
A
to (0.77)(20 atm)
C
Ao
= --------- = ----------------------------------------
RT (0.082 atm lit/mol.K)(2700 K)

- dC
A
dt
X
A


0
95
1 dX
k
1
= --------------------------------------- ------------------------------------
(151 x 10
-6
s)(0.0696 mol/lit) 0.195 – 1.195XA – 399 X
A
2



Dengan hukum Simpson dengan h = 0.008 to obtain

1
](X) = ---------------------------------
0.195 – 0.195 X – 399 X
2



h
f(X)dX = ---- [ f(Xo) + 4 f(X1) + f (X2) ]
3

ketika Xo = 0 - - - f(Xo) = 5.128

X
1
= 0.008 - - - f(X
1
) = 6.25

X
2
= 0.016 - - - f(X
2
) = 13.56
0.016


0
0.008
k
1
= 9.51 x 10
4
-------- 5.128 + 4(6.25) + 13.56 dm
3
/mol.sec
3

= 1.11 x 10
4
dm
3
/mol.sec