Introduction Arrhenius Law Collision Theory Transition State Theory

TEMPERATURE DEPENDENT TERM

Temperature Dependent Term

Temperature dependent terms that have been developed:

Arrhenius Law
Collision Theory

Transition State Theory

Temperature Dependent Term

Arrhenius, a Swedish Chemist, proposed that the temperature dependence of the reaction rate constant, kA, could be correlated by an equation:
ko = frequency factor or pre-exponential factor E = activation energy (J/mol or cal/mol) R = gas constant T = absolute temperature

Temperature Dependent Term

Activation Energy
Minimum energy that must be possessed by reacting molecules before the reaction will occur Difference between average energy of those molecules that do react and the average energy of all molecules Just an empirical parameter relating the reaction rate constant to temperature = fraction of the collisions between molecules that attain the activation energy

Temperature Dependent Term

Experimental Determination of E
The activation energy can be determined experimentally by carrying out the reaction at several different temperatures and determining the rate constants, kA, at these temperatures. To determine E, first linearize the Arrhenius Equation

Temperature Dependent Term

Temperature Dependent Term

Features of Arrhenuis equation (Levenspiel)

A plot of k vs 1/T gives a straight line, with a large slope for large E, small slope for small E. Reactions with high activation energies are very temperature sensitive; reactions with low activation energies are relatively temperature-insensitive.

Temperature Dependent Term

(Levenspiel)

Temperature Dependent Term

Collision Theory
Originally based on the kinetic theory of gases reaction occurs when:
Molecules collide Possess enough energy to undergo transformation Rate of reaction = (frequency of collision) x (fraction of collisions that have energy to react)

Temperature Dependent Term

How to derive the frequency of collision?

Consider:

A and B are rigid spheres of radii A and B, respectively. A moves at a relative velocity UR. B
B
A UR B

Temperature Dependent Term

Collision is assumed when A touches B, with a collision radius (AB =A and B) within a collision area S =(A and B ) 2.
B A

Temperature Dependent Term

Distance traveled by molecule A = URt At time t, A sweeps a volume V, equal to:

AB A UR

Temperature Dependent Term

While A sweeps out this volume, it will undergo collisions with B within this volume. Number of collisions is:

AB A

UR B B

Temperature Dependent Term

From kinetic theory of gases:

Where:

Therefore, the frequency of collision of all molecules A is:

Temperature Dependent Term

Rate of reaction (with respect to number of molecules reacting) = (frequency of collision) x (fraction of collisions that have energy to react)

Using Avogadros number:

Temperature Dependent Term

Temperature Dependent Term

Transition State Theory

Reactants combine to form unstable intermediates called activated complexes, which decompose to products spontaneously, or revert back to reactants. Schematic representation:

Temperature Dependent Term

Final form of reaction rate:

K =Boltzman constant H = Planck constant QABC,QA,QB = partition functions per unit volume Eo = energy change going from reactants to products

Temperature Dependent Term

Arrhenius Law Collision Theory Transition State Theory

The fraction of collision term is more sensitive than the Tm term, thus, the variation due to Tm term is masked.

Introduction Intermediates Reaction Schemes Testing of Mechanisms and Models Examples of Reaction Mechanisms

KINETIC MODELS

Kinetic Models
Kinetics of non-elementary reactions are explained using the following assumption: The overall reaction of a nonelementary reaction can be written as a sequence of elementary reactions (reaction mechanism). The sequence may postulate the appearance of intermediates, which cannot be measured or observed as they are in very minute quantities.

Kinetic Models

Reaction mechanism/ kinetic model

The * represents unobserved intermediates.

INTERMEDIATES AND REACTION SCHEMES

Kinetic Models
Intermediates Types of intermediates which may be postulated in a reaction mechanism:
Free Radicals Contains an unpaired electron

Ion or Polar Substances

Electrically charged atoms or molecules

Molecules Transition Complexes

Short life span Unstable forms of molecules having strained bonds or unstable associations which either decompose to give products or return to molecules in the normal state

Kinetic Models
Reaction Schemes Non-chain reactions Chain Reactions
Generally consists of sequences
Initiation
Active intermediate initially formed

Propagation
Active intermediate is propagated (increased formation) with simultaneous product formation

Termination
Active intermediate is destroyed by transformation into more stable products

Kinetic Models

Initiation Propagation*

Termination
propagation is an essential feature Intermediate is not consumed but acts as a catalyst

*the

EXAMPLES OF REACTION MECHANISMS

Kinetic Models

The Kinetic Model/Reaction mechanism can be expressed/ named from the type of intermediate and reaction scheme
Non-chain reactions
Molecules Transition Complexes

Chain reactions
Free radicals

Kinetic Models

Free Radical, Chain Reaction

Mechanism:

Kinetic Models

Molecular Intermediate, Non-chain Reaction

Mechanism

Kinetic Models

Transition Complex, Non-chain Reaction

Mechanism: H2 + I2

H I 2HI

H I

H I

H I

TESTING OF POSTULATED REACTION MECHANISM

Kinetic Models
Given a reaction and experimental rate law which is not elementary, we can attempt to propose a reaction mechanism to explain the nonelementary algebraic expression of the rate law. To check if the proposed reaction mechanism is correct, the theoretical rate law must be similar to the experimental rate law.

Kinetic Models

How?
Answer:

Obtain the theoretical rate laws from the proposed reaction mechanism and apply the steady-state approximation.

Kinetic Models
1.

From the reaction mechanism, set-up the elementary rate law of the target component (reaction product or reactant)
rA = will include expressions involving concentrations of intermediates.

Apply the steady state approximation. 3. Substitute CI back to the rate law obtained in (1), and simplify. 4. Compare the derived/ theoretical rate law with the experimental rate law. If analogous, the postulated reaction mechanism is correct.
2.

Kinetic Models

Consider:

Kinetic Models

Use Rules-of-thumb:

Kinetic Models

Proposal: