Chemical Kinetics

Meeting 1.
Johnson N. Naat
 Chemical Kinetics

Kinetika Kimia adalah bidang kimia yang mengkaji

kecepatan atau laju terjadinya reaksi kimia

Laju reaksi adalah Perubahan konsentrasi reaktan atau

produk terhadap waktu (M/s).

A B
[A] [A] = change in concentration of A over
rate = -
t time period t
[B] [B] = change in concentration of B over
rate =
t time period t
Because [A] decreases with time, [A] is negative.

13.1
 A B

time

[A]
rate = -
t

[B]
rate =
t

13.1
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

393 nm Detector
light
[Br2]  Absorption
13.1
Br2 (aq) + HCOOH (aq) 2Br– (aq) + 2H+ (aq) + CO2 (g)

slope of
tangent
slope of
tangent slope of
tangent

[Br2] [Br2]final – [Br2]initial

average rate = – =–
t tfinal - tinitial

13.1
 rate  [Br2]
rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10–3 s–1

13.1
 Reaction Rates and Stoichiometry

2A B

Two moles of A disappear for each mole of B that is formed.

1 [A] [B]
rate = – rate =
2 t t

aA + bB cC + dD

1 [A] 1 [B] 1 [C] 1 [D]

rate = – =– = =
a t b t c t d t

13.1
Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

[CH4] 1 [O2] [CO2] 1 [H2O]

rate = – =– = =
t 2 t t 2 t

13.1
 Hukum Laju
Konstanta laju (k) yaitu konsentrasi kesebandingan
(proporsional) antara laju reaksi dan konsentrasi reaktan

aA + bB cC + dD

Rate = k [A]x[B]y

reaction is xth order in A

reaction is yth order in B
reaction is (x + y)th order overall

13.2
 F2 (g) + 2ClO2 (g) 2FClO2 (g)

Determine x and y in the rate law Rate = k [F2]x[ClO2]y

Double [F2] with [ClO2] held constant:
The rate doubles
Therefore, x = 1

Quadruple [ClO2] with [F2] held constant:

The rate quadruples
Therefore, y = 1 The rate law is
Rate = k [F2]1[ClO2]1
13.2
 Rate Laws
• Rate laws are always determined experimentally.

• Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced
chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2] 1

13.2
 Determine the rate law and calculate the rate constant for
the following reaction from the following data:
S2O82– (aq) + 3I– (aq) 2SO42– (aq) + I3– (aq)

Initial Rate
Experiment [S2O82 – ] –
[I ] (M/s) rate = k [S2O82–]x[I–]y
1 0.08 0.034 2.2 x 10–4 y=1
2 0.08 0.017 1.1 x 10–4 x=1
rate = k [S2O82–][I–]
3 0.16 0.017 2.2 x 10–4

Double [I–], rate doubles (experiment 1 & 2)

Double [S2O82–], rate doubles (experiment 2 & 3)

rate 2.2 x 10–4 M/s

k= = = 0.08/M•s
[S2O8 ][I ] (0.08 M)(0.034 M)
2– –

13.2
 First-Order Reactions
[A]
A product rate = - rate = k [A]
t
[A]
rate M/s – = k [A]
k= = = 1/s or s-1 t
[A] M
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0

[A] = [A]0exp(–kt) ln[A] = ln[A]0 – kt

13.3
 2N2O5 4NO2 (g) + O2 (g)

k = 5.714 X 10–4 s–1

13.3
 The reaction 2A B is first order in A with a rate
constant of 2.8 x 10–2 s–1 at 800C. How long will it take for
A to decrease from 0.88 M to 0.14 M ?

ln[A]t = ln[A]0 – kt [A]0 = 0.88 M

[A]t = 0.14 M
kt = ln[A]0 – ln[A]
[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10 s–2 –1

13.3
 Half-Life of First-Order Reactions
Waktu-paruh (t½): Waktu yang diperlukan agar konsentrasi
reaktan turun menjadi setengah dari konsentrasi awal.
t½ = t when [A] = [A]0/2

[A]0
ln
[A]0/2 ln2 0.693
t½ = = =
k k k
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10–4 s–1?
t½ = ln2 = 0.693
= 1200 s = 20 minutes
k 5.7 x 10 s
–4 –1

How do you know decomposition is first order?

units of k (s-1) 13.3
 Half-Life of a First-Order Reaction

The half-life of a first-order reaction stays the same.

 Second-Order Reactions

Reaksi orde kedua: reaksi yang lajunya bergantung pada

konsentrasi salah satu reaktan dipangkatkan dua atau pada
konsentrasi dua reaktan berbeda yang masing-masing
dipangkatkan satu.
 Second-Order Reactions
[A]
A product rate = - rate = k [A]2
t

rate M/s [A]

k= = 2 = 1/M•s
– = k [A]2
[A] 2 M t

1 1 [A] is the concentration of A at any time t

= + kt
[A] [A]0 [A]0 is the concentration of A at time t=0

t½ = t when [A] = [A]0/2

1
t½ =
k[A]0

13.3
 Half-Lives of Second-Order Reactions

Each half-life is double the time of the previous half-life.

 Zero-Order Reactions
[A]
A product rate = - rate = k [A]0 = k
t

rate [A]
k= = M/s – =k
[A] 0
t

[A] is the concentration of A at any time t

[A] = [A]0 – kt
[A]0 is the concentration of A at time t = 0

t½ = t when [A] = [A]0/2

[A]0
t½ =
2k

13.3
 Half-Lives of a Zero-Order Reaction

Each half-life is ½ the time of the previous half-life.

Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k

1 rate = k [A] ln[A] = ln[A]0 - kt t½ = ln2

k
1 1 1
2 rate = k [A] 2 = + kt t½ =
[A] [A]0 k[A]0

13.3
Comparison of Graphs for H2O2 Decomposition

The reaction is
second order
with rate law
Rate = k[H2O2]2
From www.sparknotes.com
 A+B AB++ C+D
Exothermic Reaction Endothermic Reaction

activation energy (Ea ): Jumlah minimum energi yang

diperlukan untuk mengawali reaksi kimia.
13.4
 Ketergantungan konstanta laju terhadap suhu

k = A • exp( -Ea / RT )
(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the absolute temperature
A is the frequency factor
frekuensi tumbukan
Ea 1
ln k = - + lnA
R T

For Two Temperatures: ln(k1/k2) = Ea/R(1/T2 – 1/T1)

13.4
 Ea 1
lnk = - + lnA
R T

Y-Intercept = lnA

Slope = –Ea/R

13.4