10/10/2012

Reaction Rates
Combustion

Corrosive

By : Nuniek Herdyastuti
Oktober - 2012

Definition of Reaction Rate

Thermodynamics does a reaction take place?
Kinetics how fast does a reaction proceed?
Reaction rate is the change in the concentration of a reactant
or a product with time (M/s).
A

Before reaction

rate = -

[A]
t

[A] = change in concentration of A over

time period t

rate =

[B]
t

[B] = change in concentration of B over

time period t

After 10 s

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time

rate = -

[A]
t

rate =

[B]
t

2Br- (aq) + 2H+ (aq) + CO2 (g)

Br2 (aq) + HCOOH (aq)

time

393 nm
light

Detector
[Br2] a Absorption

Br2 (aq) + HCOOH (aq)

2Br- (aq) + 2H+ (aq) + CO2 (g)

Faktor yang Mempengaruhi Laju Reaksi

slope of
tangent

average rate = -

[Br2]

=-

slope of
tangent

Konsentrasi
Molekul - molekul harus bertumbukan agar terjadi reaksi
dalam konteks ini laju reaksi proporsional dengan
konsentrasi reaktan
Luas permukaan zat
Makin luas permukaan, maka tumbukan makin banyak,
sehingga reaksi makin cepat
Suhu
molekul harus bertumbukan dengan energi yang cukup
untuk bereaksi
Penambahan katalis
Katalis dapat menurunkan energi aktivasi (energi minimum
yang diperlukan agar suatu reaksi kimia dapat
berlangsung. Penambahan katalis akan mempercepat
reaksi

slope of
tangent

[Br2]final [Br2]initial
tfinal - tinitial
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Effect of reactant concentrations on rate of reaction

sodium thiosulfate, Na2S2O3, in acidic solution and sodium
arsenite, Na3AsO3

Apa pengaruh
konsentrasi terhadap
laju?

laju = k [Br2]
k=

laju
[Br2]

= konstanta laju

= 3,50 x 10-3 s-1

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The Rate Law

The rate law expresses the relationship of the rate of a reaction to
the rate constant and the concentrations of the reactants raised to
some powers.
aA+bB

Rate laws are always determined experimentally

Reaction order is always defined in terms of reactant (not
product) concentrations

cC+dD

The order of a reactant is not related to the stoichiometric

coefficient of the reactant in the balanced chemical
equation

Rate = k [A]x[B]y

reaction is xth order in A

F2 (g) + 2ClO2 (g)

reaction is yth order in B

reaction is (x +y)th order overall

rate = k [F2][ClO2] 1
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2FClO2 (g)

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F2 (g) + 2ClO2 (g)

2FClO2 (g)

Menentukan hukum laju dan menghitung konstanta laju

reaksi dari data berikut ini:
S2O82- (aq) + 3I- (aq)
2SO42- (aq) + I3- (aq)

rate = k [F2]x[ClO2]y

[F2] meningkat dua kali dan [ClO2] konstan

Laju meningkat dua kali

x=1

Percobaan

[S2O82-]

[I-]

Laju Awal
(M/s)

0,08

0,034

2,2 x 10-4

0,08

0,017

1,1 x 10-4

0,16

0,017

2,2 x 10-4

laju = k [S2O82-]x[I-]y
y=1
x=1
laju = k [S2O82-][I-]

[I-] meningkat dua kali, laju menjadi dua kali (percobaan 1 & 2)

[ClO2] meningkat empat kali dan [F2] konstan

y=1
Laju meningkat empat kali

[S2O82-] meningkat dua kali, laju menjadi dua kali (percobaan 2 & 3)
k=

rate = k [F2][ClO2]

2,2 x 10-4 M/s

laju
=
= 0,08/M s
2[S2O8 ][I ] (0,08 M)(0,034 M)

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Menentukan Orde Reaksi dengan Percobaan

Jika diketahui reaksi :

O2 (g) + 2 NO(g)

First Order Rate Law

2 NO2 (g)

Hukum laju untuk reaksi ini adalah : laju = k [O2]m [NO]n

Percobaan

Konsntrasi Reaktan awal

(mol / L)

Laju awal
(mol/L . s)

1
2
3

O2
1,10 x 10-2
2,10 x 10-2
1,10 x 10-2

NO
1,30 x 10-2
1,30 x 10-2
2,60 x 10-2

3,21 x 10-3
6,40 x 10-3
12,8 x 10-3

4
5

3,30 x 10-2
1,10 x 10-2

1,30 x 10-2
3,90 x 10-2

9,60 x 10-3
28,8 x 10-3
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Laju Reaksi - by Nuniek UNESA

product
ln[A] = ln[A]0 - kt

Tentukan persamaan laju reaksinya !

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Second Order Reactions

Zero Order Reactions
A
[A]
rate = t
- d[A]
[A]2

product
A

product

rate = -

= k [A]2

[A]
t

= k [A]0 = k
-

= k dt

[A]
t

=k

[A] = [A]0 - kt

1
1
=
+ kt
[A]
[A]0

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Summary of the Kinetics of Zero Order, First Order

and Second Order Reactions

Half Life of a Reaction (t )

The half-life, t, is the time required
for the concentration of a reactant to
decrease to half of its initial concentration

t = t when [A] = [A]0/2

ln
t =

[A]0
[A]0/2
k

ln 2
k

0.693
k

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TEORI TUMBUKAN

1. Reaksi kimia terjadi sebagai hasil dari

tumbukan antara molekul-molekul yang
bereaksi
2. Agar dapat bereaksi, molekul-molekul
yang bertumbukan harus memiliki
a. arah (orientasi) yang tepat
b. energi kinetik totalnya sama dengan
atau lebih besar daripada energi aktivasi,
Ea, yaitu energi minimum yang dibutuhkan
untuk memulai suatu reaksi kimia.

A+ B

AB

Exothermic Reaction

+
+

TEORI KEADAAN TRANSISI

Spesi yang terbentuk sementara oleh
molekul-molekul reaktan akibat tumbukan
sebelum nantinya akan membentuk produk
disebut keadaan transisi atau kompleks teraktifkan
Dalam keadaan transisi, ikatan-ikatan yang
lama sedang mengalami proses pemutusan dan
ikatan-ikatan yang baru mulai terbentuk.
Energi yang dibutuhkan untuk mencapai keadaan
transisi disebut energi aktivasi

C+D
Endothermic Reaction

The activation energy (Ea ) is the minimum amount of energy required to initiate
a chemical reaction.

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Reaction Mechanisms

Temperature Dependence of the Rate Constant

The overall progress of a chemical reaction can be represented at

the molecular level by a series of simple elementary steps or
elementary reactions

(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K mol)
T is the absolute temperature

The sequence of elementary steps that leads to product formation

is the reaction mechanism.
2NO (g) + O2 (g)

2NO2 (g)

N2O2 is detected during the reaction!

A is the frequency factor

Elementary step:
Elementary step:

NO + NO
N 2 O2 + O2

N 2 O2
2NO2

Overall reaction:

2NO + O2

2NO2

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Intermediates are species that appear in a reaction mechanism

but not in the overall balanced equation.

Rate Laws and Elementary Steps

Unimolecular reaction

An intermediate is always formed in an early elementary step and

consumed in a later elementary step
Elementary step:

NO + NO

N 2 O2

+ Elementary step:

N 2 O2 + O2

2NO2

Overall reaction:

2NO + O2

2NO2

Bimolecular reaction

A+B

products
products

rate = k [A]
rate = k [A][B]

Bimolecular reaction

A+A

products

rate = k [A]2

Writing plausible reaction mechanisms:

The sum of the elementary steps must give the overall
balanced equation for the reaction.

The molecularity of a reaction is the number of molecules

reacting in an elementary step

The rate-determining step should predict the same rate law

that is determined experimentally.

Unimolecular reaction elementary step with 1 molecule

Bimolecular reaction elementary step with 2 molecules

The rate-determining step is the slowest step in the

sequence of steps leading to product formation.

Termolecular reaction elementary step with 3 molecules

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The experimental rate law for the reaction between NO2 and
CO to produce NO and CO2 is rate = k[NO2]2. The reaction is
believed to occur via two steps:
Step 1:

NO2 + NO2

Step 2:

NO3 + CO

NO + NO3
NO2 + CO2

What is the equation for the overall reaction?

NO2+ CO

NO + CO2

What is the intermediate? NO3

What can you say about the relative rates of steps 1 and 2?
rate = k[NO2]2 is the rate law for step 1 so
step 1 must be slower than step 2
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A catalyst is a substance that increases the rate of a chemical

reaction without itself being consumed
k = A . exp( -Ea / RT )

Ea

Katalis adalah zat yang meningkatkan laju reaksi

tanpa ikut terpakai dalam reaksi

Uncatalyzed

Catalyzed

Katalis bekerja dengan cara mengubah mekanisme.

Mekanisme yang baru ini mempunyai energi aktivasi
yang rendah
Katalis mempercepat reaksi baik ke arah kiri
maupun kanan dan tidak dapat meningkatkan hasil
setimbang akhirnya, namun dapat mempercepat
tercapainya keadaan setimbang akhir

ratecatalyzed > rateuncatalyzed

Ea< Ea

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Haber Process

In heterogeneous catalysis, the reactants and the catalysts are

in different phases.
Haber synthesis of ammonia
Ostwald process for the production of nitric acid
Catalytic converters
In homogeneous catalysis, the reactants and the catalysts are
dispersed in a single phase, usually liquid.
N2 (g) + 3H2 (g)

Acid catalysis

Fe/Al2O3/K2O
catalyst

2NH3 (g)

Base catalysis

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Enzyme Catalysis

See You !!!!!!

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