Introduction to

Reaction Engineering
Kinetics
Explore the fundamental concepts of reaction kinetics, from determining rate
laws to understanding the impact of temperature and catalysts.

by JAYESH IITK
Determination of Rate Laws
Experimentally
Initial Rate Method Integral Method
Measure initial reaction rates at different reactant Analyze concentration vs. time data to determine
concentrations. rate law.

Differential Method Reaction Progress Method

Calculate reaction rates from concentration vs. Follow reaction progress over time to find rate
time data. law.
Initial Rate Integral Method Differential Reaction
Method Method Progress Method
Experimental Techniques for Kinetic
Studies
1. Batch Reactor Experiments:  Measuring product formation over time to determine reaction rate and order.
2. Continuous Flow Reactor Studies:  Analyzing inlet and outlet concentrations to extract kinetic parameters.

3. Stopped-Flow Techniques: ⏱ Rapid mixing and detection methods for fast reactions.

4. Temperature-Jump Experiments:  Inducing a rapid temperature change to probe transient kinetics.

5. Spectroscopic Monitoring: ú Using in-situ optical, NMR, or mass spectrometry to track reactions.
Interpretation of Kinetic Data
Graphical Analysis 1
Plot reaction rate vs. time, concentration,
or temperature to identify order and rate
constants. 2 Linear Regression
Linearize data to determine reaction order
and rate constants from slope and
Nonlinear Regression 3 intercept.
Fit kinetic model to data to extract rate
constants and activation energy.
Reaction Order and Rate Constants
Understanding the order of a reaction and its associated rate constant is crucial in reaction kinetics. The order
describes the dependence of the rate on reactant concentrations.

Determining the reaction order experimentally allows us to develop rate laws and predict how changes in
reactant concentrations will affect the overall rate.

The rate constant reflects the intrinsic speed of the reaction and is temperature-dependent according to the
Arrhenius equation.
Temperature Dependence of
Reaction Rates
Factors Affecting Reaction Rates
1 Temperature, pressure, concentration, and catalyst presence

Exponential Relationship
2 Reaction rate increases exponentially with temperature

Arrhenius Equation
3 Quantifies temperature dependence of reaction rates
Temperature Dependence of Reaction
Rates
Arrhenius Equation and Activation Energy
The Arrhenius equation describes the temperature
dependence of reaction rates.

It relates the rate constant to the activation energy

and absolute temperature.

Activation energy is the minimum energy required for

a reaction to occur.

Catalysts lower the activation energy, increasing the

reaction rate.
Reaction Mechanisms and Elementary
Steps

Reactants
1 Molecules that interact to form products

Elementary Steps
2
Fundamental reaction steps involving a few molecules

Reaction Mechanism
3 Sequence of elementary steps that describe the
overall reaction

Understanding the reaction mechanism, which is the sequence of fundamental steps that describe how reactants
are converted into products, is crucial for optimizing reaction conditions and improving process efficiency. By
analyzing the elementary steps involved, we can gain insights into the kinetics, thermodynamics, and potential
pathways of the overall reaction.
Reaction Pathway Analysis
Identify Reactants
1
Determine the starting molecules

Propose Intermediates
2
Hypothesize the formation of key compounds

Determine Kinetics
3
Study the rates of each step

Validate Mechanism
4
Confirm the proposed reaction pathway

Reaction pathway analysis is a crucial step in understanding the mechanism of a chemical reaction. It involves
identifying the reactants, proposing possible intermediates, determining the kinetics of each step, and validating
the overall reaction mechanism through experimental data and theoretical modeling.
Steady-State Approximation and Kinetic
Modeling

2 30K
Key Steps Kinetic Expressions
Identify rate-determining step, apply steady-state Derive differential equations for species
assumption concentrations

Steady-state approximation simplifies complex reaction mechanisms. Identify the rate-determining step and
apply the steady-state assumption to derive kinetic expressions. Develop differential equations to model species
concentrations over time.
Catalysts and their Effect on Reaction
Kinetics

Reaction Acceleration Mechanistic Changes Kinetic Parameters

Catalysts lower activation energy, Catalysts alter the reaction Catalysts impact rate constants,
dramatically increasing reaction pathway, enabling different reaction orders, and activation
rate. mechanisms. energy.
Inhibitors and their Impact on Reaction
Rates

Enzyme Inhibitors Reduced Reaction Experimental Competitive

Rates Observations Inhibition
Molecules that bind to
enzymes and block their Inhibitors lower the Carefully measure the Inhibitors that compete
catalytic activity overall rate of a chemical impact of inhibitors on with reactants for
reaction kinetics binding sites
Diffusion and Mass Transfer Limitations
Diffusion Mass Transfer Concentration Pore Diffusion
Challenges Barriers Gradients
Restricted access in
Slow transport of Boundary layers hinder Depletion of reactants porous catalysts
reactants to active sites exchange with bulk at reaction interface
fluid
Heterogeneous Catalysis and Kinetics
Heterogeneous catalysts have complex surface structures that interact with reactants.

Kinetics of heterogeneous catalysis depend on adsorption, surface reactions, and desorption.

Diffusion of reactants and products to and from the catalyst surface is crucial.

Catalyst deactivation by poisoning or fouling can significantly impact reaction kinetics.

Mechanism Reaction Steps Kinetic Expressions

Langmuir-Hinshelwood Adsorption, Surface Reaction, Rate = k θA θB / (1 + θA + θB)

Desorption

Eley-Rideal Adsorption, Gas-Ads. Reaction, Rate = k [A]gas θB / (1 + θB)

Desorption

Mars-van Krevelen Red. of Catalyst, Reaction, Ox. of Rate = k [A]gas [O]catalyst / (1 +

Catalyst [A]gas)
Applications of Reaction Engineering
Kinetics

1 Chemical Process Optimization 2 Product Development

Improve efficiency and yields by Design new chemical products by modeling
understanding reaction kinetics reaction mechanisms

3 Environmental Remediation 4 Energy Conversion

Analyze kinetics of pollutant degradation for Optimize catalytic processes for fuel cells,
clean-up solutions biofuels, and more