Teknik Reaksi Kimia 1:

Reaksi Molekuler
ENCH605021 – 3 SKS

Muhammad Ibadurrohman, Ph.D (DIC)

Introduction

• The understanding on the kinetics of chemical reactions

is approached by considering chemical interactions on
molecular level
• Two theories have been deemed successful in
qualitatively explaining the phenomena, namely:
• Collision Theory
• Transition State Theory
Introduction
Cato
• Efforts to comprehend the nature of reaction kinetics can Maximilian
be traced back to 1864, when Guldberg and Waage Guldberg
proposed the Law of Mass Action (1836 - 1902)
• Law of Mass Action dictates that the rate of a chemical
reaction is directly proportional to the product of the
activities or concentrations of the reactants
• The law is a statement about equilibrium and gives an
expression for the equilibrium constant
• Any chemical reaction following this law is what we now call
elementary reaction
• This law, however, only views chemical reactions on
macroscopic level
Peter Waage
(1833 - 1900)
Collision Theory
Max Trautz
• Collision theory was idependently proposed by Trautz in (1880 - 1960)
1916 and Lewis in 1918, viewing the molecules of
reactants as rigid spheres that collide with each other,
allowing interactions
• This theory assumes that:
• There is no intermolecular interaction unless the
molecules make direct physical contacts to each other
• The molecules retain their size and shape whilst colliding,
and they do not penetrate to each other
• Intermolecular interaction is established when the
interaction manages to rearrange valence electrons and
overcome the energy barrier to reach a lower energy
(more stable) state William Lewis
(1885 - 1956)
Collision Theory
• Collision theory explains:
• Why different reactions occur at different rates
• Ways to change the rate of a reaction
• Collision theory states that:
• Reacting particles must collide to initiate reaction
• Particles that collide do not necessarily react
• The only case when collision leads to reaction is when the reacting
particles collide with sufficient energy, and with proper
orientation
Collision Theory
• Requirement 1: Particles must collide to react

𝐴 + 𝐵 → products 𝑟 = 𝑘 𝐴 [𝐵]

How about termolecular reaction?

Collision Theory
Fritz Haber
• Requirement 1: Particles must collide to react (1868 - 1934)
Consider an example of Haber-Bosch process
(ammonia production):
𝑁2 (𝑔) + 3𝐻2 (𝑔) ֞ 2𝑁𝐻3 (𝑔)

The collision theory says that 𝑁2 and 𝐻2 will only react

when they collide.
• More frequent collisions constitute faster reaction
• Increasing reaction rate by:
• Increasing gas pressure
Carl Bosch
• Increasing temperature (1874 - 1940)
Collision Theory
• Requirement 1: Particles must collide to react
Mathematical models that describe collision frequency bear these assumptions
(although technically these statements are false in general):
• All molecules travel through space in straight lines
• All molecules are hard, rigid spheres
• The reaction of interest is between only two molecules
• Collision are either hit or miss only
Collision frequency is affected by:
• Temperature
• Density
• Size of reacting molecules
Collision Theory
• Requirement 1: Particles must collide to react
Collision frequency of two molecules of the same species 𝐴, 𝑍𝐴𝐴 is evaluated as follows:
2
2 2 𝑁 8𝑘𝐵 𝑇
𝑍𝐴𝐴 = 𝜋𝑑
2 𝑉 𝜋𝑚
Where:
𝑍𝐴𝐴 = collision frequency (m-3s-1)
𝑑 = molecule diameter of 𝐴 (m)
𝑘𝐵 = Boltzmann constant (1.38 × 10−23 J.K-1)
𝑚 = mass of molecule (kg)
𝑁 = number of 𝐴 molecules
𝑉 = volume of the system (m3)
𝑇 = temperature (K)
Collision Theory
• Requirement 1: Particles must collide to react
Collision frequency of two different molecules 𝐴 and 𝐵, 𝑍𝐴𝐵 is evaluated as follows:
8𝜋𝑘𝐵 𝑇
𝑍𝐴𝐵 = 𝑁𝐴 𝑁𝐵 (𝑟𝐴 + 𝑟𝐵 )2
𝜇𝐴𝐵
Where:
𝑍𝐴𝐵 = collision frequency (m-3s-1)
𝑟𝐴 , 𝑟𝐵 = molecule radius of 𝐴 and 𝐵, respectively (m)
𝑁𝐴 , 𝑁𝐵 = number of 𝐴 and 𝐵 molecules, respectively
𝑚𝐴 𝑚𝐵
𝜇𝐴𝐵 = reduced mass =
𝑚𝐴 + 𝑚𝐵
𝑚𝐴 , 𝑚𝐵 = mass of molecules 𝐴 and 𝐵, respectively (kg)
Collision Theory

• Requirement 1: Particles must collide to react

Collision frequency of a single molecule 𝑖 in one second is evaluated as follows:

𝑁 8𝑘𝐵 𝑇
𝑍𝑖 = 2𝜋𝑑2
𝑉 𝜋𝑚

Where:

𝑍𝑖 = collision frequency of a single molecule 𝑖 (m-3s-1)

Collision Theory
• Requirement 2: Particles must collide with sufficient energy
Ineffective collision, not enough
energy to initiate reaction

Effective collision, enough energy t

o initiate reaction

• The minimum energy required to initiate reaction is termed activation

energy (𝑬𝑨 ).
• Any chemical reaction results in the breaking of some bonds (needing
energy) and the making of new ones (releasing energy). Some bonds
have to be broken to introduce new ones. Activation energy is involved
in breaking the bonds
Collision Theory
• Requirement 2: Particles must collide with sufficient energy

𝐸𝐴
𝐸𝐴
Collision Theory
• Requirement 2: Particles must collide with sufficient energy
• Reversible reaction
Collision Theory
• Requirement 2: Particles must collide with sufficient energy
Collision Theory
James
• Requirement 2: Particles must collide with Maxwell
sufficient energy (1831 - 1879)

Ludwig
Boltzmann
Maxwell-Boltzmann Distribution (1844 - 1906)
Collision Theory
• Requirement 2: Particles must collide with sufficient energy

Maxwell-Boltzmann Distribution
Collision Theory
• Requirement 2: Particles must collide with sufficient energy
Collision Theory
• Requirement 2: Particles must collide with sufficient energy
Collision Theory
• Requirement 3: Particles must collide with proper orientation
• Even if the collisions are frequent and highly energetic,
reactions do not occur unless the collisions take place in a way
that the molecules are properly orientated.
• When the molecules collide with the right orientation, so that
the proper atoms line up with one another, and bonds can
break and re-form in a necessary fashion
• Molecules in liquid and gas phase are in constant, random
motion so there is always probability that two molecules collide
in just the right way
Collision Theory
• Requirement 3: Particles must collide with proper orientation
Consider the reaction between nitric oxide and ozone:
Collision Theory
• Requirement 3: Particles must collide with proper orientation
Consider the reaction between ethylene and HCl producing chloroalkane:

The probability of reaction on the basis of its chemical structure is

termed steric factor, denoted by 𝑃 where 0 ≤ 𝑃 ≤ 1
Arrhenius Equation
Req 1
Req 3
𝐸𝐴 Req 2
𝑘 = 𝑃𝑍𝐴𝐵 exp −
𝑅𝑇

𝑘 = rate constant (M-1s-1) The product 𝑃𝑍𝐴𝐵 is usually denoted

𝑃 = steric factor as a pre-exponential factor 𝐴:
𝑍𝐴𝐵 = collision frequency (M-1s-1)
𝐸𝐴 = activation energy (kJ.mol-1) 𝐸𝐴
𝑅 = gas constant (kJ.mol-1.K-1) 𝑘 = 𝐴 exp −
𝑅𝑇
𝑇 = temperature (K)
Arrhenius Equation
Determining the activation energy:

𝑘 = 𝐴𝑒 −𝐸𝐴/𝑅𝑇
Taking natural logarithm of both sides results in:
𝐸𝐴 𝟏
𝐥𝐧 𝒌 = ln 𝐴 −
𝑅 𝑻

𝑦 = 𝑐 + 𝑚𝒙
It only takes two rate constants at two different temperature to calculate
activation energy
Arrhenius Equation
Consider an example of isomerisation of cyclopropane to propene:

From the calculated slope, activation energy is calculated as

follows:
Arrhenius Equation
1. The rate constant for the decomposition of N2O5 to NO and O2 in the gas
phase is 1.66 L/mol/s at 650 K and 7.39 L/mol/s at 700 K.
2𝑁2 𝑂5 → 4𝑁𝑂 + 3𝑂2

Calculate the activation energy for this decomposition!

2. What is the Activation Energy of a reverse reaction at 679 K if the forward

reaction has a rate constant of 50 M-1s-1, a pre-exponential factor of 30 M-1s-1​,
and a ΔG of reaction of 23 kJ/mol?
 Transition State Theory
• Although widely used to calculate the energy barrier for reactions, the Arrhenius
equation fail to explain mechanistic aspects of the reaction, mostly due to the fact that it
derives from empirical observations
• Information pertaining to, for instance, whether one or more reactive intermediates are
involved in the conversion of reactant to product, was omitted
• In 1935, Eyring, Evans, and Polanyi proposed the Transition State Theory (TST), a.k.a.
“activated complex theory”, absolute-rate theory, and “theory of absolute reaction rates”

Meredith Evans
(1904 - 1952)

Michael
Henry Eyring Polanyi
(1901 - 1981) (1891 - 1976)
Transition State Theory
TST explains the kinetics of elementary reactions, which is based on the idea
that a molecular collision that leads to reaction must pass through an
intermediate state known as the transition state. For example, the reaction:
𝐴 + 𝐵𝐶 → 𝐴𝐵 + 𝐶

would have an intermediate (𝐴 − 𝐵 − 𝐶) where the bond 𝐵 − 𝐶 is partially

broken, and the bond 𝐴 − 𝐵 is partially formed:

𝐴 + 𝐵𝐶 ֞ (𝐴 − 𝐵 − 𝐶)‡ → 𝐴𝐵 + 𝐶

The double-dagger symbol ‡ denotes an activated complex

Transition State Theory

∆𝐺 ‡
𝐸𝐴 of catalysed
reaction

∆𝐺 does not
change
Transition State Theory
Transition State Theory
Transition State Theory
Transition State Theory

𝐶‡
𝐴‡
𝐵‡
𝐵 𝐶
𝐴
𝐷
Eyring Equation
𝐾‡ 𝑘‡
‡
𝐴 + 𝐵𝐶 ֞ (𝐴 − 𝐵 − 𝐶) → 𝐴𝐵 + 𝐶

Reaction rate: Decomposition of activated complexes:

𝑟 = 𝑘 𝐴 𝐵𝐶 = 𝑘 ‡ [(𝐴 − 𝐵 − 𝐶)‡ ] 𝑘𝐵 𝑇
𝑟‡ = 𝑣 𝐴 − 𝐵 − 𝐶 ‡ = 𝐴−𝐵−𝐶 ‡
Quasi-equilibrium of transition state: ℎ
𝑘𝐵 𝑇
[(𝐴 − 𝐵 − 𝐶)‡ ] 𝑘‡ = ∆𝐺 ‡ = −𝑅𝑇 ln 𝐾 ‡
𝐾‡ = ℎ
𝐴 𝐵𝐶
𝑘𝐵 𝑇 ‡ 𝑘𝐵 𝑇 ∆𝐺 ‡
𝑟 = 𝑘 ‡ 𝐾 ‡ 𝐴 𝐵𝐶 𝑘= 𝐾 𝑘= exp −
ℎ ℎ 𝑅𝑇
𝑘 = 𝑘 ‡𝐾 ‡
Eyring Equation
𝑘𝐵 𝑇 ∆𝐺 ‡ 𝑘𝐵 𝑇 ∆𝑆 ‡ ∆𝐻 ‡
𝑘= exp − = exp exp −
ℎ 𝑅𝑇 ℎ 𝑅 𝑅𝑇

𝑘 = rate constant (M-1s-1)

𝑘𝐵 = Boltzmann constant (1.38 × 10−23 J.K-1) ∆𝐺 ‡ = ∆𝐻 ‡ − 𝑇∆𝑆 ‡
ℎ = Planck constant (6.63 × 10−34 m2.kg.s-1)
∆𝐺 ‡ = Gibbs energy of activation (J)
∆𝐻‡ = Enthalpy of activation (J)
∆𝑆 ‡ = Entropy of activation (J)
𝑇 = temperature (K)
Eyring Equation
Determining the enthalpy of activation:

𝑘𝐵 𝑇 ∆𝑆 ‡ ∆𝐻‡
𝑘 = exp exp −
ℎ 𝑅 𝑅𝑇
Taking natural logarithm of both sides results in:
𝒌 ∆𝐻‡ 𝟏 𝑘𝐵 ∆𝑆 ‡
𝐥𝐧 = − + ln +
𝑻 𝑅 𝑻 ℎ 𝑅

𝑦 = −𝑚𝒙 + 𝑏
It only takes two rate constants at two different temperature to calculate
enthalpy of activation
 ‡
𝑬𝑨 vs ∆𝑯
Arrhenius equation: Eyring equation:

𝐸𝐴 𝑘𝐵 𝑇 ∆𝑆 ‡ ∆𝐻 ‡
𝑘 = 𝐴 exp − 𝑘 = exp exp −
𝑅𝑇 ℎ 𝑅 𝑅𝑇
Taking natural lof of both sides and taking Taking natural lof of both sides, taking
differential with resperct to 𝑇, and differential with resperct to 𝑇, and
rearranging : rearranging :

d ln 𝑘 𝐸𝐴 d ln 𝑘 1 ∆𝐻 ‡
= = +
𝑑𝑇 𝑅𝑇 2 𝑑𝑇 𝑇 𝑅𝑇 2

𝐸𝐴 = ∆𝐻 ‡ + 𝑅𝑇
Transition State Theory
• Mathematical formulations derived from TST is, in general, more reliable than
those derived from collision theory.

• TST is, however, limited by the fact that tunnelling could occur to bypass the
energy barrier (especially in the case of low 𝐸𝐴 ), as stipulated by quantum
mechanics

• Transition state theory assumes that an equilibrium exists between the

reactants and the transition state phase. However, in solution non-equilibrium
situations can arise, upsetting the theory