1

Kinetika Reaksi
2
Kinetika Reaksi
) ( ) (
2
3
) (
2
1
3 2 2
g NH g H g N +
Contoh
) ( ) (
2
1
) (
2 2 2
l O H g O g H +
1
/

A mol kJ G
o
r
-16.63
-237.19
Termodinamik: energi dan spontanitas reaksi
Termodinamik: tidak dapat menjawab (1) bagaimana reaksi
berlangsung (2) berapa cepat reaksi berlangsung (3) mekanisme
reaksi
Reaction
Kinetics
3
Kinetika Reaksi
) ( ) (
2
3
) (
2
1
3 2 2
g NH g H g N +
) ( ) (
2
1
) (
2 2 2
l O H g O g H +
T, P, katalis
T, katalis
Kinetika kimia:
Kinetika kimia
Mempelajari laju dan mekanisme reaksi dari reaksi kimia
Reaction
Kinetics
4
Laju reaksi
Reaksi homogen:

b
a
dt dn
dt dn
B
A
=
/
/
+ + + + fF eE bB aA
Laju konversi
dt
dn
f dt
dn
e dt
dn
b dt
dn
a
J
F E B A
1 1 1 1
= = = =
dt
dn
b dt
dn
a
B A
1 1
=
Reaction
Kinetics
5
Laju Reaksi
|
.
|

\
|
=
dt
dn
a V V
J
r
A
1 1
= = = = = =
dt
F d
f dt
E d
e dt
B d
b dt
A d
a
r
] [ 1 ] [ 1 ] [ 1 ] [ 1
Laju reaksi, r
mol dm
-3
s
-1
mol cm
-3
s
-1
Reaction
Kinetics
6
Hukum Laju
Untuk beberapa
reaksi
| | | | | |
| o
L B A k r =
k: konstanta laju, k = f (T, P)
o, |, .: orde reaksi
o+| + . + n : orde keseluruhan
Reaction
Kinetics
7
Orde Reaksi
o
k r =
| | A k r =
| |
2
A k r =
| || | B A k r =
| | | | B A k r
2
=
| || |
2
B A k r =
| || |
2
= B A k r
| || |
2 / 1
B A k r =
| || | | | ( )
2 / 1
1 / B B A k r =
Zero-order
First-order
Second-order
Third-order
Negative First-order
1.5-order
No simple order
Reaction
Kinetics
8
Hukum laju
Reaksi Hukum Laju
HBr Br H 2
2 2
+
| || |
| | | |
2
2 / 1
2 2
/ 1 Br HBr j
Br H k
r
+
=
2 2 5 2
4 2 O NO O N +
HI I H 2
2 2
+ | || |
2 2
I H k r =
| |
5 2
O N k r =
CO CH CHO CH +
4 3
| |
2 / 3
3
CHO CH k r =
Reaction
Kinetics
9
Mekanisme Reaksi
3 2 2
SO NO SO NO + +
2 2
2 2 NO NO O +
3 2 2
2 2 SO O SO
NO
+
intermediate
2 2 5 2
4 2 O NO O N +
3 2 5 2
NO NO O N +
2 3
2NO NO NO +
2 2 3 2
NO O NO NO NO + + +
Tahap (a)
Tahap(b)
Tahap (c)
Elementary
reaction
Reaction
Kinetics
10
Pengukuran Laju Reaksi
Metode Kimia
The concentration of a reactant or product as a function of time
Reaction vessels
At constant T
At intervals
Slows down or stop
the reaction
Rapidly analyze chemical
compositions of the mixture
Cooling the sample
removing a catalyst
Diluting the mixture
Adding a species
Reaction
Kinetics
11
Metode Fisika
Measures a physical property of the reaction system as a
function of time. This allows the reaction to be followed
continuously as it proceeds.
More accurate and less tedious
Reaction
Kinetics
12
Integrasi Laju Reaksi
Assumptions
(a) The reaction is carried out at constant temperature (k is constant)
(b) The volume is constant (r is given by (17.4))
(c) The reaction is irreversible (k
o
is very large)
= = = = = =
dt
F d
f dt
E d
e dt
B d
b dt
A d
a
r
] [ 1 ] [ 1 ] [ 1 ] [ 1
Integrate it to find [A] as a function of time: [A] = g(t)
Reaction
Kinetics
13
Reaksi Orde Satu
Suppose the reaction
P aA
is first-order with
| | A k r =
= = = = = =
dt
F d
f dt
E d
e dt
B d
b dt
A d
a
r
] [ 1 ] [ 1 ] [ 1 ] [ 1
| | | | | |
| o
L B A k r =
| |
| | A k
dt
A d
a
r = =
1
define
ak k
A
| | | | A k dt A d
A
= /
| | | | dt k A A d
A
= /
| | | |
}
=
}
2
1
2
1
/ dt k A A d
A
Reaction
Kinetics
14
| | | |
}
=
}
2
1
2
1
/ dt k A A d
A
| | | | ( ) ) ( / ln
1 2
1 2
t t k A A
A
=
| |
| |
t k
A
A
A
o
= ln
if
t t =
2
| | | |
o
A A =
1
at
0
1
= t | | | | A A =
2
at and
| | | |
t k
o
A
e A A

=
The concentration of A (and r) decreases exponentially with
time for a first-order reaction.
| |
| | A k
dt
A d
a
r = =
1
Integrated rate law
Reaction
Kinetics
15
First-order reaction: ln[A] vs t
| | | |
t k
o
A
e A A

=
| | | | t k A A
A
o
= ln ln
[
A
]
/
[
A
]
o

t
First-order reaction: [A]/[A]
o
vs t
| |
| |
t k
o
A
e
A
A

=
L
n
[
A
]

t
| | | | t k A A
A
o
= / ln
Reaction
Kinetics
16
2 / 1
t
Half-life:
2 / 1
t t =
o
A A ] [ 2 / 1 ] [ =
| |
| |
t k
A
A
A
o
= ln
2 / 1
] [
] [ 2 / 1
ln t k
A
A
A
o
o
=
693 . 0 2 ln
2 / 1
= = t k
A
First-order reaction
2 / 1
2 / 1 ln t k
A
=
The time needed for [A] to drop to half its value
A
k t / 693 . 0
2 / 1
=
Independent of [A]
o

A useful indication for the chemical reaction rate
Reaction
Kinetics
17
Second-Order Reactions
2
2
2
] [A P 2A ) 2 (
A][B] [ P B A ) 1 (
k r
k r
=
= +
| |
| |
2
1
A k
dt
A d
a
r = =
define
ak k
A

| | | |
2
/ A k dt A d
A
=
| |
| |
2
A k
dt
A d
A
=
| |
| |
}
=
}
2
1
2
1
2
1
dt k A d
A
A
Reaction
Kinetics
18
Second-Order Reactions
| | | |
) (
1 1
1 2
2 1
t t k
A A
A
=
A plot of 1/[A] versus t gives a strait line of slope k
A

if
ak k
A

| |
| |
| |
o
A
o
A t k
A
A
+
=
1
| |
| |
}
=
}
2
1
2
1
2
1
dt k A d
A
A
| | | |
t k
A A
A
o
=
1 1
| |
2
A k r =
Reaction
Kinetics
19
{[A]
-1
}
{t}
Second-order reaction: 1/[A] vs t
Second-Order Reactions
| | | |
t k
A A
A
o
=
1 1
| | | |
t k
A A
A
o
+ =
1 1
2 / 1
t
Half-life:
2 / 1
t t =
o
A A ] [ 2 / 1 ] [ =
A o
k A
t
] [
1
2 / 1
=
Second-order reaction with
r = k[A]
2

Reaction
Kinetics
20
Second-Order Reactions
A o
k A
t
] [
1
2 / 1
=
Second-order reaction with r = k[A]
2

A
k
t
2 ln
2 / 1
=
First-order reaction with r = k[A]
products bB aA +
| || | B A k r =
| |
| || | B A k
dt
A d
a
=
1
Three variables
Reaction
Kinetics
21
Second-Order Reactions
products B A +
0 = t
| |
| || | B A k
dt
A d
=
x=0 when t=0
| |
o
A | |
o
B
t t = | | x A
o

| | x B
o

0
x
| |
| || | | | ( ) | | ( ) x B x A k B A k
dt
A d
o o
= =
| |
dt
dx
dt
A d
=
| | ( ) | | ( ) x B x A k
dt
dx
o o
=
| | ( ) | | ( )
kdt
x B x A
dx
o o
=

| | ( ) | | ( )
}
=
}

t x
o o
kdt
x B x A
dx
0 0
Reaction
Kinetics
22
Second-Order Reactions
| | ( ) | | ( )
kt kdt
x B x A
dx
t x
o o
=
}
=
}

0 0
| | ( ) | | ( ) | | | | | | ( ) | | ( )
dx
x B x A A B x B x A
dx
x
o o o o
x
o o
}
)
`

=
}

0 0
1 1 1
| | | |
| |
| |
| |
| |

)

|
|
.
|

\
|

|
|
.
|

\
|

=
x B
B
x A
A
A B
o
o
o
o
o o
ln ln
1
| | | |
| |
| |
| |
| |
kt
x B
B
x A
A
A B
o
o
o
o
o o
=

|
|
.
|

\
|

|
|
.
|

\
|

ln ln
1
| | | |
| | | |
| | | |
kt
A A
B B
A B
o
o
o o
=
|
|
.
|

\
|
/
/
ln
1
| | | | x A A
o
=
| | | | x B B
o
=
Reaction
Kinetics
23
Second-Order Reactions
| | ( ) | | ( )
| | ( )
kt kdt
x A
dx
x B x A
dx
t x
o
x
o o
=
}
=
}

=
}

0 0
2
0
| | ( )
| | | |
kt
A x A
x A
dx
o o
x
o
=

=
}

1 1
0
2
If [A]
o
=[B]
o
| | | |
kt
A A
o
=
1 1
2 / 1
t
Half-life:
2 / 1
t t =
o
A A ] [ 2 / 1 ] [ =
| |
o
A k
t
1
2 / 1
=
Reaction
Kinetics
24
Third-Order Reactions
| |
| |
3
A ak
dt
A d
=
| |
| |
dt k
A
A d
A
=
3
| | | |
t k
A A
A
o
2
1 1
2 2
=
| |
| | | | B A ak
dt
A d
2
=
| |
| || |
2
B A ak
dt
A d
=
| |
| || || | C B A ak
dt
A d
=
(Problems 17.17 and 17.24)
| |
| |
| | ( )
2 / 1
2
2 1
o
o
A kt
A
A
+
=
Reaction
Kinetics
25
nth-Order Reaction
Consider
| |
1
) 1 (
n
o
A n
| |
| |
n
A
A k
dt
A d
=
Integration gives
| |
| |
}
=
}
2
1
2
1
dt k
A
A d
A
n
| | | |
t k
n
A A
A
n
o
n
=
+

+ +
1
1 1
For n = 1
| |
| |
| | t k n A
A
A
A
n
o
n
o
) 1 ( 1
1
1
+ =
|
|
.
|

\
|

For n = 1
Reaction
Kinetics
26
nth-Order Reaction
| |
A
n
o
n
k A n
t
1
1
2 / 1
) 1 (
1 2

=
For n = 1
| | | |
t k
o
A
e A A

= For n = 1
2 / 1
t
Half-life:
2 / 1
t t =
o
A A ] [ 2 / 1 ] [ =
A
k
t
2 ln
2 / 1
=
| |
| |
}
=
}
2
1
2
1
dt k
A
A d
A
n
| | | | t k A A
A o
=
| |
A
o
k
A
t
2
2 / 1
=
For n = 0
Reaction
Kinetics