19/09/2017

General Chemistry 1
PCC-12303

Lecture 3
Chemical kinetics

Last week: the second law

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The second law

The second law

• The second law of thermodynamics determines the direction of
processes: entropy increases !
• For chemical reactions, we need to consider entropy change of
the system and of the surroundings (due to heat exchange)
• This is accounted for by the Gibbs reaction energy:
∆ ∆ ∆

∆ 0 : reaction goes to right

∆ 0 : reaction goes to left
∆ 0 : equilibrium
Josiah W. Gibbs
1839 - 1903

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“…if your theory is found to be against

the Second Law of Thermodynamics, I
an give you no hope; there is nothing
for it but to collapse in deepest
humiliation.”

Sir. Arthur Eddington

Example: oxidation of organics

Combustion of sucrose:

+ 12 O2 12 CO2 + 11 H2O

⦵
∆ 5640 kJ/mol
⦵
∆ 512 J/mol · K
⦵
∆ 5640 298 0.512
5793 kJ/mol

Why does sugar not burn spontaneously?

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Kinetic barriers

Gibbs
energy
Sucrose +
oxygen

Carbon
dioxide +
water

The second law of thermodynamics is time’s arrow,

but chemical kinetics is time’s variable clock

The rate of chemical reactions

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Example

NO g $ CO& g → NO& g $ CO (g)

+ +

Example

Gas-phase oxidation of HBr:

4 HBr g $ O& g → 2 Br& g $ 2 H& O (g)

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Outline

• The reaction rate

• The effect of concentration: the reaction order
o Determining the reaction order
• Collision theory
o Kinetic barriers
• The mechanism of a reaction

The rate of a reaction

2 SO. g → 2 SO& g $ O& (g)
Concentration (mol/L)

SO3

Time (s)

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The rate of a reaction

2 SO. g → 2 SO& g $ O& (g)
1 / SO3 1 / SO2 / O2
1
Concentration (mol/L) 2 /0 2 /0 /0

SO3 SO2

O2

Time (s)

Varying the initial concentration

2 SO. g → 2 SO& g $ O& (g)

[SO3] (mol/L) r (mol L-1 s-1)

0.01 1.0 1034
0.02
[SO3]0=0.03 M 4.0 1034
[SO3]0=0.03 M
[SO3]0=0.03 M
0.03 9.0 1034

Rate law: 1 2 SO3 p 2

1 2 SO3
Reaction order Second order

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Example: Haber process

N& (g) $ 3 H& g → 2NH. g
1 2 N2 p H2 q

[N2] [H2] r (mol L-1 s-1)

(mol/L) (mol/L)
0.01 0.01 1.0 1034
0.02 0.01 1.0 1034
0.01 0.02 2.0 1034
What are the reaction orders p and q of the reactants ?

Example
N& (g) $ 3 H& g → 2NH. g
1 2 N2 p H2 q

[N2] [H2] r (mol L-1 s-1)

(mol/L) (mol/L)
0.01 0.01 1.0 1034
p=0
0.02 0.01 34
1.0 10
0.01 0.02 2.0 1034

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Example
N& (g) $ 3 H& g → 2NH. g
1 2 N2 p H2 q

[N2] [H2] r (mol L-1 s-1)

(mol/L) (mol/L)
0.01 0.01 1.0 1034
0.02 0.01 1.0 1034 q=1
0.01 0.02 2.0 1034

1 2 N2 0 H2 1 2 H2

Reaction order is not determined by coefficients in overall reaction !

Reaction orders
Simple reaction: A products
Rate law: /A p
1 2A
/0
• 6 0 : zeroth order

• 6 1 : first order

• 6 2 : second order

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Zeroth order reaction

Simple reaction: A products
Rate law: /A
1 2 A A 7 20
/0
Integrated
[A] rate law

08/& t

First order reaction

Simple reaction: A products
Rate law: /A
1 29A: A A 7 ; 3<=
/0

[A] ln[A]

08/& t t

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Second order reaction

Simple reaction: A products
Rate law: /A 1 1
1 29A:& $ 20
/0 A A7

[A] 1
A

08/& t t

Example: carbon dating

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Example: carbon dating

Example

What is the rate law ?

(a) 1 29NO2:7 (b) 1 29NO2:8 (c) 1 29NO2:&

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Towards equilibrium

brown colorless

Equilibrium: still color left

Towards equilibrium

Equilibrium:
Forward rate: 18 138
18 28 NO2 2
28 NO2 2 238 N2O4
Backward rate:
138 238 N2O4 N2O4 28
?
NO2 2 238

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The rate of reactions

A+B C+D
1 2A p B q found from experiments

But what happens at the molecular scale ?

Collisions

Reaction rate: 1 A B C

# collisions fraction with fraction with

per second correct enough
orientation energy

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Collision frequency
A+B C+D
Reaction rate: 1 D B C

Number of A-B collisions per second per m3:

AEF G H 9I:

P
Depends on: • J KL ~ N /O
• molecular radii, 1E , 1F

Orientation factor
A+B C+D
Reaction rate: 1 A R C
Orientation factor: 0 B 1

What reaction has the largest value for P ?

(a) H (g) + Cl (g) HCl (g)

(b) NO (g) + CO2 (g) NO2 (g) + CO (g)

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Energy factor
A+B C+D
Reaction rate: 1 A B S
Transition
state

Energy

Progress of reaction

The activation energy

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Activation energy
A+B C+D

intermediate
Energy

A+B TU

∆T~∆
C+D

Progress of reaction

Activation energy
A+B C+D
Boltzmann distribution Z[ ~; 3V\ /XY
Number of molecules

C ; 3VW /XY
Molecules with
enough energy

TU Energy level

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Effect of temperature
A+B C+D
Boltzmann distribution

Number of molecules
Higher T
C ; 3VW /XY

TU Energy level

The rate equation

A+B C+D
Reaction rate: 1 A B C
GB 3V /XY
; W H 9I:
ZE

TU 2 H; 3VW /XY
ln 2 ln H
N

Svante Arrhenius
1859-1902

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The effect of temperature

The “activation energy” of pizza

T (˚C) Storage k (1/s)
time (days)
4 2 5.8 103^
-6 7 1.6 103^
-12 30 3.9 103^
-18 100 1.2 103_

ln 2 TU
ln 2 ln H
Slope: N
TU
1.12 103` (K)
N
TU 93 kJ/mol
1/T (1/K)

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Intermezzo

Ben Feringa, Nobel Prize 2016

Intermezzo

Manipulating energy barriers with light !

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The mechanism of a reaction

4 HBr g $ O& g → 2 Br& g $ 2 H& O (g)

The overall reaction equation says nothing about

how the molecules collide !

A possible mechanism:
Intermediates
(1) HBr g $ O& g → HOOBr (g)
(2) HOOBr g $ HBr g → 2 HOBr (g)
(3) HOBr g $ HBr g → Br& g $ H& O g 9 2:

Elementary reactions
Molecularity: number of reactant molecules

Elementary step Molecularity Rate law

A → products Unimolecular r = k[A]
2A → products Bimolecular r = k[A]2
A + B → products Bimolecular r = k[A][B]
2A + B → products Termolecular r = k[A]2[B]

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What is the overall rate?

A → B → C → D

The rate-determining step

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The rate-determining step

A → B → C → D
What step is rate-limiting ?
Which intermediate is easier to detect?
Energy

A
B
C

D
Progress of reaction

The rate-determining step

4 HBr g $ O& g → 2 Br& g $ 2 H& O (g)
A possible mechanism:
(1) HBr $ O& → HOOBr 18 28 HBr 9O2:

(2) HOOBr $ HBr → 2 HOBr 1& 2& HOOBr 9HBr:

(3) HOBr $ HBr → Br& $ H& O 9 2: 1. 2& HOBr 9HBr:

Step (1) is the slowest. What is the overall rate equation ?

1 2 9HBr:b O& c 1 28 HBr 9O2:

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Example
NO& g $ CO (g) → NO g $ CO& g
&
Observed rate equation: 1 2 NO&

(1) 2 NO& g → NO. g $ NO g slow

(2) NO. g $ CO (g) → NO& g $ CO& g fast

What is the rate-limiting step ?

Another example

2 1
potential energy

reaction progress

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Another example
(1) 2 NO g ⇌ N& O& g fast equilibrium
(2) N& O& g $ H& g ⟶ N& O g + H& O g slow
(3) N& O g $ H& g ⟶ N& g + H& O g fast

What is the overall reaction ?

2 NO g $ 2 H& g $ ⟶ N& g + 2 H& O g

Another example
(1) 2 NO g ⇌ N& O& g fast equilibrium
(2) N& O& g $ H& g ⟶ N& O g + H& O g slow
(3) N& O g $ H& g ⟶ N& g + H& O g fast

What is the rate equation ?

& &
(a) 1 2 NO (c) 1 2 9H& : NO

(b) 1 29 H& :& NO (d) 1 2[H& : NO

1 2 f H& N& O& 29H& : NO &

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Catalysis

Catalysts speed up a reaction

Enzymes

Heterogeneous catalysts

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Example: the Ozone layer

Catalysis: the Ozone layer

UV
O. g ⟶ O& g + O g Paul Crutzen
Nobel prize 1995
Destruction of ozone in upper atmosphere:
Energy

O. g $ O g ⟶ 2O& g slow +
2
In the presence of halogen atoms
Catalyzed pathway
+
(from photodissociation of CFCs):

O. g $ Cl g ⟶ ClO g $ O& g
fast !
ClO g $ O g ⟶ Cl g $ O& g

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Catalysis: the Ozone layer

16 September 1987

Summary

• The rate law: 1 29A:b 9B:c

• Chemical reactions = molecular collisions followed by

atom rearrangements

• Effect of temperature: Arrhenius law

• Reaction mechanisms: rate-limiting step

• Catalysis

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Thanks !

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