KINETIKA KIMIA

BAMBANG WIDIONO
KINETIKA KIMIA ? "how fast do reactions
go?"
Untuk apa ? ( manfaat )
Matakuliah terkait ? ( matematika,
stoikiometri, … )
 What is Chemical Reaction Engineering
(CRE) ?
Understanding how chemical reactors work lies at the heart of
almost every chemical processing operation.

Products
Raw Separation Chemical Separation
material Process process Process By products

Design of the reactor is no routine matter, and many alternatives can

be proposed for a process. Reactor design uses information,
knowledge and experience from a variety of areas -
thermodynamics, chemical kinetics, fluid mechanics, heat and mass
transfer, and economics.

CRE is the synthesis of all these factors with the aim of properly
designing and understanding the chemical reactor.
 Typical Chemical Process
Unit Operations

Physical Chemical Physical

Raw treatment treatment treatment Products
materials steps steps steps

• pre-treatment • separations
• purifications

REACTION ENGINEERING
 Book
• O.Levenspiel: “Chemical Reaction
Engineering”
• S.Fogler: “Elements of Chemical
Reaction Engineering”
• J M Smith : “ Chemical Engineering
Kinetics “
• Stanley M Walas : “ Chemical Reaction
Engineering Handbook”
 persamaan reaksi tidak dapat
menjawab 3 isu penting

1. Seberapa cepat reaksi berlangsung

2. Bagaimana konsentrasi reaktan dan produk
saat reaksi selesai
3. Apakah reaksi berjalan dengan sendirinya
dan melepaskan energi, ataukah ia
memerlukan energi untuk bereaksi?
 Kinetika kimia
• Studi tentang kecepatan reaksi kimia dan
faktor-faktor yang mempengaruhinya serta
mekanisme reaksi
 Classification of Reactions
Many ways of classification
Most useful - according to number & types of phases
Homogeneous: reaction takes place in 1 phase
Heterogeneous: reaction REQUIRES at least 2 phases

Phase = uniform P,T, Composition

According to the use / not use of catalyst

Noncatalytic
Catalytic
 Classification of Reactions
Noncatalytic Catalytic

Most gas-phase reactions Most liquid-phase rxs

Homogeneous
Fast reactions such as Rxs in colloidal systems
burning of a flame
Enzyme and microbial rxs

Burning of coal Ammonia synthesis

Heterogeneous
Oxidation of ammonia
Attack of solids by acids
produce to nitric acid
Gas-liquid absorption
with reaction
 Mengekspresikan Laju Reaksi
Perubahan posisi x2  x1 x
Laju Gerak   
Perubahan waktu t 2  t1 t
Perubahan konsentrasi A
Laju reaksi 
Perubahan waktu
Konst A 2  Konst A1 ( Konst A)
 
t 2  t1 t

 A  B 
Laju   
t t
 How can reaction rate be
expressed ?

• Select one reaction component for

consideration and define the rate in terms
of this component, i.
• If the rate of change in number of moles of
this component due to reaction is dNi/dt,
then the rate of reaction in its various
forms is defined as follows:
 Reaction Rate Definition

• the rate at which a species looses its chemical identity per unit volume

 For fluid systems - based on unit volume of fluid / unit volume of reactor

1 dN i moles i formed 1 dN i moles i formed

ri   ri  
V dt (volume of fluid) (time) Vr dt (volume of reactor) (time)

 For gas-solid systems - based on unit volume of solid

1 dN i moles i formed
ri''  
VS dt (volume of solid) (time)
 Reaction Rate Definition

 For 2 fluid systems / gas-solid system - based on unit interfacial surface

1 dN i moles i formed
ri S  
S dt (surface) (time)

 For fluid-solid systems - based on unit mass of solid

1 dN i moles i formed
ri w  
W dt (mass of solid) (time)

riV  Wri w  Sri S  VS ri''  Vr ri '

 Speed of Chemical Reactions

human
at rest
10-4 10-3 10-2 0.1 1 10 104

cellular rxs. working gases in porous rocket

hard catalyst particles engines
 water
treatment plants

moles of i disappearing
ri'' 
(m 3 of thing) (s)
 Reaction Rate – example 1

 The rocket engine:

• burning a stoichiometric mixture of fuel (lq. hydrogen & oxygen)
• Cylindrical combustion chamber: L=75cm, D=60cm
• Produces 108 kg/s exhaust gases

Reaction rate of
hydrogen and oxygen?
 Reaction rate – example 1

1 dN H 2 D 2  (0.6) 2
 rH 2  V L (0.75)  0.2121 m 3
V dt 4 4
?
1 dN O2 1
 rO2  H 2  O2  H 2O
V dt 2

kmol
kg 108 (kg / s ) H 2 used : 6
108 H 2O   6 kmol / s s
s 18 (kg / kmol ) kmol
O2 used : 3
s
1 6 kmol moles 1 3 kmol moles
 rH 2   2.8 10 4 3  rO2   1.41 10 4 3
0.2121 s m s 0.2121 s m s
 The Rate Equation / Stoichiometry

aA  bB  cC  dD
1 dN A
 rA  rate of disappearance of A
V dt
1 dN

r 
C
V dt
C
rate of appearance of C

Relationship  rA  rB rC rD
between rates of   
reaction a b c d
 Reaction Rates and Reaction
Stoichiometry

• Look at the reaction

O3(g) + NO(g)  NO2(g) + O2(g)

d O 3  d[NO] d[ NO 2 ] d[ O 2 ]
rate = - =- =+ =+
dt dt dt dt
 Another Example
2 NOCl (g)  2 NO + 1 Cl2 (g)

1 d NOCl  1 d[NO] d[Cl 2 ]

rate = - = =+
2 dt 2 dt dt

WHY? 2 moles of NOCl disappear

for every 1 mole Cl2 formed.
 Relationship between rates of
reaction
The reaction carried out in a reactor:
2 A  3B  5C
                   
If at a particular point, the rate of disappearance of A is 10 mol/dm3/s, what
are the rates of B and C?

 rA 10 mol mol
 rB  3 3  15
 rA  rB rC 2 2 dm3  s dm3  s
 
2 3 5  rA 10 mol mol
 rC  5 5  25
2 2 dm3  s dm 3  s
 Kecepatan reaksi
• Kecepatan reaksi diekspresikan :

rate=change in substance/time for change to occur (usually in M/s)

To increase the rate :

• increasing the surface area (of solids)-this allows for more collisions and gives
more molecules the right geometry

• increasing the temperature-this gives more molecules the right energy (also
called the activation energy, Ea)

• increasing the concentration (of gases and solutions)-this allows for more
collisions and more correct geometry
• using a catalyst-helps molecules achieve the correct geometry by providing a
different way to react

• The physical state (solid, liquid or gas) of a reactant

• Nature of reactants - Na is more reactive than Ca (it more easily loses its
outer electron)
 Luas Permukaan Sentuhan
• Suatu reaksi mungkin banyak melibatkan
pereaksi dalam bentuk padatan
• Mengapa kepingan yang lebih halus bereaksi
lebih cepat? Pada campuran pereaksi yang
heterogen, reaksi hanya terjadi pada bidang
batas campuran yang selanjutnya kita sebut
bidang sentuh. Oleh karena itu, makin luas
bidang sentuh makin cepat bereaksi. Jadi makin
halus ukuran kepingan zat padat makin luas
permukaannya.
• Artinya makin kecil ukuran, makin luas
permukaannya, makin banyak tumbukan, makin
cepat terjadinya reaksi
 The effect of increasing temperature

• When the temperature is raised the added 'heat energy'

shows itself in the form of increased particle kinetic energy.
In the graph above, two distribution curves are shown for a
lower/higher temperatures, T1/T2, and it is assumed that the
area under the whole curve is the same for both
temperatures i.e. the same number/population of molecules.
• Comparing lower temperature T1 with higher temperature T2, you can see that as
the temperature increases, the peak for the most probable KE is reduced, and more
significantly with the rest of the KE distribution, moves to the right to higher values so
more particles have the highest KE values.

• Now, if we consider an activation energy Ea, the minimum KE the particles must
have to react via e.g. bond breaking, the fraction of the population able to react at T1
is given by the blue area.

• However, at the higher temperature T2, the fraction with enough KE to react is given
by the combined blue area plus the red area.

• Therefore, because of the shift in the distribution at the higher temperature T2, a
greater fraction of particles has the minimum KE to react and hence a greater chance
of a fruitful collision happening i.e. reactant molecule bonds breaking en route to
product formation.

• In the diagram, for the sake of argument, a temperature rise from T1 to T2 results in
the fraction of particles with a KE of >=Ea being doubled (area blue==>blue+red).

• For reactions with an activation energy in the range 50-100 kJmol-1 (i.e. most
reactions), this results in an approximately  doubling of the reaction rate for every 10o
rise in temperature i.e. where T2 = T1 + 10, because if you double the number of
particles of KE >= Ea, you therefore double the chance of a fruitful collision and hence
double the rate of reaction.
 The effect of a catalyst

• A catalyst speeds up a reaction, but it must be

involved 'chemically', however temporarily, in
some way, and is continually changed and
reformed as the reaction proceeds.
• Catalysts work by providing an alternative reaction pathway of lower
activation energy, e.g. it can assist in endothermic bond breaking
processes

• If you consider the KE distribution curve above, at a fixed

temperature, the green area shows the molecules which have
sufficient KE to react and overcome the activation energy Ea1 for
the un-catalysed reaction.

• However, in the presence of a catalyst, the lower activation energy

Ea2, allows a much greater proportion of the molecules to have
enough energy to react at the same temperature.

• This is shown by the combined green area plus the purple area
and this increased fraction of molecules (increased area)
considerably increases the chance of a 'fruitful' collision leading to
product formation, so speeding up of the reaction.
 Catalysis
Catalyst: a substance that increases the
rate of a reaction and can be recovered
chemically unchanged at the end of the
reaction.
A catalyst
Lower the activation energy

• Katalis dapat bekerja dengan membentuk

senyawa antara atau mengabsorpsi zat
yang direaksikan.
 Activation energies of catalysed
reactions

Reaction Catalyst Ea / kJmol-1

2 HI  H 2  I 2 None 184
Au 105
Pt 109

2 NH 3  N 2  3H 2 None 350
W 162
 kONSENTRASI
• Bila konsentrasi pereaksi diperbesar
dalam suatu reaksi, berarti kerapatannya
bertambah dan akan memperbanyak
kemungkinan tabrakan sehingga akan
mempercepat laju reaksi.
• Bila partikel makin banyak, akibatnya lebih
banyak kemungkinan partikel saling
bertumbukan yang terjadi dalam suatu
larutan, sehingga reaksi bertambah cepat.
 MEKANISME REAKSI
• serangkaian reaksi tahap demi tahap yang
terjadi berturut-turut selama proses
perubahan reaktan menjadi produk.
• Setiap tahap mekanisme reaksi diatas,
mempunyai laju tertentu. Tahap yang
paling lambat disebut tahap penentu laju
reaksi, karen tahap ini merupakan
penghalang untuk laju reaksi secara
keseluruhan.
Conc. / Temp. dependency terms

r  f (conc., temp.)

 rA  [k (T )][ f (C A , C B ,...)]
Reaction rate Concentration
(constant) dependent terms
Persamaan umum:
aA + bB + ... ----> gG + hH + .....

• the reaction rate can be calculated by:

Reaction rate = k[A]m[B]n ....
Dengan:
• [A], [B], etc. are the concentrations of the reactants
k is the rate constant or rate coefficient, a value
dependent on temperature. units of k=
units of rate/(units of concentration) reaction order
• m,n, etc. are exponents which correspond to a, b, etc.
The concentration is raised to the power of its coefficient
in the balanced equation.
 Rate constant (k)

 rA  k[ f (C A , C B ,...)]
Dimensions vary with order of reaction (n):

(time) 1 (concentration)1 n

CA -rA Reaction order Rate law k

(mol/m3) (mol/m3.s) zero  rA  k (mol/m3)/s

(mol/m3) (mol/m3.s) 1st  rA  kC A 1/s

(mol/m3) (mol/m3.s) 2nd  rA  kC A2 (m3/mol)/s

 Arrhenius' Equation

k=Ae-Ea/RT
• Where:
• A is a constant related to the geometry
needed
e is a constant, approximately 2.7281
Ea is the activation energy
R is the gas law constant, 8.314 J/mol-K
T is the temperature in kelvins
 Temperature, Rates & the
Arrhenius Equation
• One can calculate the rate constant for a reaction using the
Arrhenius equation:
 Ea / RT
k  Ae
• A is a constant representing the fraction of collisions between
molecules having the correct orientation to react when the
reactants have a concentration of 1 M. It is generally not known.
• But A can be factored out if one ratios the equation at two
temperatures. One typically uses this modified Arrhenius
equation to either calculate Ea values from rate constants
derived from experiments at different temperatures, or a rate
constant at a different temperature if one has already determined
E a.
  k 2  Ea  1 1 
ln      
 k1  R  T1 T 2 
k2
R ln
k1
Ea 
 1 1 
T T 
 1 2
 Concentration-dependent term

 rA  k[ f (C A , C B ,...)]
Almost without exception determined by experimental observation!!!

Most common expression:

  
 rA  kC C ....C
A B D

Order of reaction:  order in A

 order in B
n      ...  overall order
 Elementary / Non-elementary
Reactions

A B  C  D stoichiometric coeff: a  b  c  d 1

 Elementary reactions – iff stoichiometric coefficients are the same as the

individual reaction order of each species

 rA  kC AC B    1

 Non-elementary reactions – stoichiometry does not match the kinetics

 rA  kC A2 C B  2
 1
 Problem:
• How much will the rate increase if a rxn
has a Ea = 70kJ/mol and the temperature
increases from 300K to 400K?

• A reaction has k = 1.6 × 10-5 s-1 at 600 K.

When the temperature is increased to
700 K the new measured k = 6.36 × 10-3
s-1. Calculate the Ea value for this
reaction.
 Common types of rate laws:
1. First Order Reactions
• In a first order reaction the rate is proportional to the concentration
of one of the reactants. That is,
v = rate = k[B],                (1)
• where B is a reactant. If we have a reaction which is known to be
first order in B, such as
B + other reactants → products,
• we would write the rate law as,
v = rate = k[B],                               (2)
• The constant, k, in this rate equation is the first order rate constant.

2. Second Order Reactions

• In a second order reaction the rate is proportional to concentration
squared. For example, possible second order rate laws might be
written as
Rate = k[B]2                (3)
or as
Rate = k[A][B].                (4)
 First Order Reaction
A  product
Rate = v = - d[A]/dt = k[A]
How does the concentration of the
reactant depend on time?

 A 
ln   kt
 Ao 
k has units of s-1
 CA
 e  kt
C A0

• Jadi persamaan hubungan konsentrasi A

dengan waktu :
C A  C A0 e  kt
• Atau bisa dinyatakan hubungan antara
konversi dengan waktu :
C A0 (1  X A )  C A0e  kt

X A 1  e kt
 Contoh soal :
• Suatu larutan A dengan konsentrasi 0,5 gmol/L
dalam reactor batch dengan volume larutan 2,5
L bereaksi membentuk B dengan persamaan
reaksi
• A B, reaksi merupakan reaksi order 1
dengan kecepatan reaksi -rA= kCA, dengan nilai
k=0,01 1/menit berapa konsentrasi A, konversi
A serta konsentrasi B setelah 3 menit :
 Penyelesaian :
• Dengan penjabaran neraca massa A seperti di
atas dipeoleh persamaan :

C A  C A0 e  kt
1
 ( 0 , 01 )( 3 menit )
gmol menit
C A  0,5 e
L  ( 0 , 01
1
menit
)( 3 menit )

C A  0,485 gmol / L X A 1  e kt X A 1 e

XA = 0,029

• CB = CB0 + CA0X = 0 + 0,5(0,029 ) = 0,0145 gmol/L

 TUGAS 1
• Suatu larutan A dengan konsentrasi 10
gmol/L dalam reactor batch dengan
volume larutan 2,5 L bereaksi membentuk
B dengan persamaan reaksi A 3B,
reaksi merupakan reaksi order 1 dengan
kecepatan reaksi rA= kCA, dengan nilai
k=0,02 1/menit berapa konsentrasi A,
konversi A serta konsentrasi B, setelah 3
menit
The Half-life of a First Order
Reaction

• For a first order reaction, the half-life t1/2

is calculated as follows.
0.693
t1 /2 
k
 Kinetika Orde dua; bentuk
integrasi
Kinetika Orde 2
2A  produk

Hukum laju: dA/dt = k[A]2

A t
dA
A [ A]2   0 kdt
0

1 1
  kt
[ A] [ A]0
1 1
  kt t
[ A] [ A0 ]
 Half-life for This Second Order
Reaction.
• [A] at t = t½ = ½ [A]0

1 1
= + kt 1 / 2
[A ]0 /2 [A ]o
1
or t 1 / 2 =
k [A ]0
• EXAMPLE: Given the following experimental kinetic data, determine the kinetic
rate expression and overall order of reaction.
• 2HgCl2 + C2O42- ------ Hg2Cl2 + 2CO2 + 2Cl-

Exp # [HgCl2] [C2O42-] 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
• Our tentative rate expression for this reaction is:
rate = k[HgCl2]x[C2O42-]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.
We can then set up the following proportionality:
y
[ A ] y
R a te (e x p # 2 ) [ A exp#2 ] exp#2
= y =
R a te (e x p # 1 ) [A e x p # 1 ] [A e x p # 1 ]
-5 y
8 x 10 0 .3 0
=
2 x 1 0 -5 0 .1 5
y
4 = (2 )
I f y o u c a n ’t s o lv e th is b y in s p e c t io n , th e n
ta k e th e lo g o f e a c h s id e o f th e e q u a tio n :
lo g (4 ) = y lo g (2 )
R e a r r a n g e a n d s o lv e fo r y :
lo g (4 ) 0 .6 0 2
y = = = 2
lo g (2 ) 0 .3 0 1
 Step #2: Repeat for the other reactant
concentration terms in the rate equation:

[A e x p # 2 ] x
R a te (e x p # 2 )
=
R a te (e x p # 3 ) [A e x p # 3 ]
-5 x
8 x 10 0 .1 0
=
-5
4 x 10 0 .0 5

(2 ) x x = 1
2 =
 Now that we have solved for the orders of the
kinetic rate expression, we can write out the
rate equation:

• rate = k[HgCl2][C2O42-]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.
ra te = k [H g C l ] [C O 2 - ] 2
2 2 4
ra te
k =
[H g C l2 ] [C 2 O 4 2 - ] 2

2 x 1 0 -5 M s e c -1
k =
(0 .1 0 M ) (0 .1 5 M ) 2
2 x 1 0 -5 M s e c -1
k =
2 .2 5 x 1 0 -3 M 3
k = 8 .8 8 x 1 0 -3 M -2 s e c -1
Problem: Consider the following reaction and
kinetic data. What is the kinetic rate
expression?
• Ni(CO)4 + CNCH3 Ni(CO)3(CNCH3) + CO

Exp # [Ni(CO)4] [CNCH3] 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) + H2O(g) CO2(g) + H2(g)

Exp [CO [H2 Initial Rate
# ] O] (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

 A Pseudo-first Order Reaction
• Example hydration of methyl iodide
CH3I(aq) + H2O(l)  CH3OH(aq) + H+
(aq) + I-(aq)
Rate = k [CH3I] [H2O]
• Since we carry out the reaction in aqueous
solution
[H2O] >>>> [CH3I]  [H2O] doesn’t
change by a lot
 Pseudo-first Order (cont’d)
• Since the concentration of H2O is
essentially constant
v = k [CH3I] [constant]
= k`[CH3I] where k` = k [H2O]
• The reaction is pseudo first order since it
appears to be first order, but it is actually
a second order process.
 Single / Multiple Reactions

 Single reaction – 1 equation & 1 single rate equation

A B  C  D
 Multiple reactions – more than 1 rate equation needed

Series reactions: A RS

Parallel reactions:
R A R A B  R
A
S BS RBS
competitive side by side series & parallel
 Physical Reaction Kinetics
Chemistry Homogeneous Catalysis
The kinetics of the bromide-catalysed decomposition of
hydrogen peroxide
2 H 2O2 (aq)  2 H 2O(aq)  O2 ( g )

The reaction is believed to proceed through the following pre-

equilibrium:
[ HOOH 2 ]
H 3O   HOOH  HOOH 2  H 2O K
[ HOOH ][ H 3O  ]

HOOH 2  Br   HOBr  H 2O r  k[ HOOH 2 ][ Br  ]

HOBr  HOOH  H 3O   O2  Br  (fast)

(in the equilibrium constant, the activity of H2O has been set equal to 1.)
d [O2 ]
 kK [ HOOH ][ H 3O  ][ Br  ]
dt
 Physical Reaction Kinetics
Chemistry Types of Homogeneous Catalysis
Heterogeneous catalysis normally depends on at least one reactant
being adsorbed (usually chemisorbed) and modified to a form in
which it readily undergoes reaction.

Acid catalysis X  HA  HX   A
Homogeneous catalysis Brønsted acid reacts
(many organic reactions) Base catalysis XH  B  X   BH 
Brønsted base reacts

Autocatalysis
The acceleration of a reaction by the products.
A P v  r[ A][ P ]

The reaction rate increases as products are formed.

 Physical Reaction Kinetics
Chemistry Autocatalysis
A P r  k[ A][ P ] Homewor
[ A]  [ A]0  x [ P ]  [ P]0  x k
The rate law No. 1
dx At what time is the reaction
 k  [ A]0  x  [ P ]0  x 
dt rate a maximum?
Integration by partial fractions, using [tmax  (1 / ka) ln b]

1 1  1 1 
    
 [ A]0  x [ P]0  x  [ A]0  [ P]0  [ A]0  x [ P]0  x 
1   [ P]0  x [ A]0 
ln   kt
[ A]0  [ P]0  [ P]0  [ A]0  x  

x e at  1 b
[ P ]0
 a  k ([ A]0  [ P]0 )
[ P ]0 1  be at [ A]0
 Physical Reaction Kinetics
Chemistry Unimolecular Reactions
The Lindemann-Hinshelwood Mechanism
The L-H mechanism proposed that a reactant molecule A becomes
energetically excited by collision with another A molecule.
d [ A* ]
A  A 
1k
A*  A  k1[ A]2
dt
The energized molecule might lose its excess energy by collision
with another A molecule.
d [ A* ]
* k2
A  A  A  A  k 2 [ A* ][ A]
dt

Alternatively, the excited molecule might shake itself apart and

form products P (it might undergo the unimolecular decay).
d [ A* ]
* k3
A  P  k3[ A* ]
dt
 Physical Reaction Kinetics
Chemistry Unimolecular Reactions
The Lindemann-Hinshelwood Mechanism
d [ A* ]
k1
A  A  A  A *  k1[ A]2
dt
d [ A* ]
* k2
A  A  A  A  k2 [ A* ][ A]
dt

d [ A* ]
k3
A*  P  k3[ A* ]
dt

The steady-state approximation to the net rate of formation of A*.

d [ A* ] k1[ A]
 k1[ A]2  k 2 [ A* ][ A]  k3[ A* ]  0 [ A* ] 
dt k3  k 2 [ A]

d [ P] k1k3[ A]2
 k3[ A* ] 
dt k3  k 2 [ A]
 Physical Reaction Kinetics
Chemistry Unimolecular Reactions
The Lindemann-Hinshelwood Mechanism
d [ P] k1k3[ A]2
 k3[ A* ] 
dt k3  k 2 [ A] This is not first-order

If the rate of deactivation by (A*, A) collision is much greater than

the rate of unimolecular decay
k 2 [ A* ][ A]  k3[ A* ] k 2 [ A]  k3

d [ P] k1k3 kk
 [ A]  k[ A] first-order k 1 3
dt k2 k2

d [ P]
k 2 [ A]  k3  k1[ A]2 second-order
dt
 Physical Reaction Kinetics
Chemistry Improvements of the Theory
RRKM Mechanism
The L-H mechanism agrees in general with the switch in order of
unimolecular reactions, but does not agree in detail.
d [ P] k1k3[ A]2
 k3[ A* ]   k[ A] 1/k
dt k3  k 2 [ A]

k1k3[ A] 1 k 1
k  2 
k3  k 2 [ A] k k1k3 k1[ A]

A plot of 1/k against 1/[A] expects to be 1/[A]

a straight line.
The graph has a pronounced curvature when a larger value of k
(small 1/k) at higher pressure (low 1/[A])
 KATALIS HETEROGEN
• Banyak logam yang dapat mengikat cukup
banyak molekul-molekul gas pada
permukannya, misalnya Ni, Pt, Pd dan V. Gaya
tarik menarik antara atom logam dengan
molekul gas dapat memperlemah ikatan kovalen
pada molekul gas, dan bahkan dapat
memutuskan ikatan itu. Akibatnya molekul gas
yang teradborpsi pada permukaan logam ini
menjadi lebih reaktif daripada molekul gas yang
tidak terabsorbsi. Prinsip ini adalah kerja dari
katalis heterogen, yang banyak dimanfaatkan
untuk mengkatalisis reaksi-reaksi gas.
 REAKSI KATALIS
• zat A dan zat B yang direaksikan membentuk zat AB
dengan zat C sebagai katalis.
ABA + B ——– (reaksi lambat)
• Bila tanpa katalis diperlukan energi pengaktifan yang
tinggi dan terbentuknya AB lambat. Namun, dengan
adanya AC (reaksi cepat).katalis C, maka terjadilah
reaksi: A + C—
• Energi pengaktifan diturunkan, AC terbentuk cepat dan
seketika itu juga AC bereaksi dengan B membentuk
senyawa ABC.
AC + B ABC (re——aksi cepat)
• Energi pengaktifan reaksi ini rendah sehingga dengan
cepat terbentuk ABC yang kemudian mengurai menjadi
AB dan C.
AB +ABC ——– C (reaksi cepat)