Chemical Kinetics - Comprehensive Short Notes
1. Introduction to Chemical Kinetics
Definition: Chemical kinetics is the study of reaction rates and the factors that affect them.
Key Concepts:
Rate of reaction: Change in concentration of reactants/products per unit time
Reaction mechanism: Step-by-step pathway by which a reaction occurs
Rate-determining step: The slowest step in a multi-step reaction mechanism
2. Rate of Reaction
Mathematical Expression: For reaction: aA + bB → cC + dD
Rate = -1/a × d[A]/dt = -1/b × d[B]/dt = 1/c × d[C]/dt = 1/d × d[D]/dt
Units: mol L⁻¹ s⁻¹ or M s⁻¹
Average vs Instantaneous Rate:
Average rate = Δ[concentration]/Δt (over a time interval)
Instantaneous rate = d[concentration]/dt (at a specific moment)
3. Factors Affecting Reaction Rate
3.1 Concentration
Higher concentration → more collisions → faster rate
Rate generally increases with increasing reactant concentration
3.2 Temperature
Higher temperature → more kinetic energy → faster rate
Rule of thumb: Rate doubles for every 10°C increase
3.3 Catalyst
Provides alternative pathway with lower activation energy
Increases rate without being consumed
Does not affect equilibrium position
3.4 Surface Area
Larger surface area → more contact → faster rate
Important for heterogeneous reactions
3.5 Pressure (for gases)
Higher pressure → higher concentration → faster rate
4. Rate Laws and Rate Constants
Rate Law: Rate = k[A]ᵐ[B]ⁿ
Where:
k = rate constant
m, n = reaction orders (determined experimentally)
[A], [B] = concentrations of reactants
Overall Order: m + n
Units of k:
Zero order: mol L⁻¹ s⁻¹
First order: s⁻¹
Second order: L mol⁻¹ s⁻¹
nth order: (mol L⁻¹)¹⁻ⁿ s⁻¹
5. Methods to Determine Rate Laws
5.1 Initial Rate Method
Measure initial rates at different concentrations
Compare rates to determine orders
5.2 Integrated Rate Laws
Zero order: [A]ₜ = [A]₀ - kt
First order: ln[A]ₜ = ln[A]₀ - kt
Second order: 1/[A]ₜ = 1/[A]₀ + kt
5.3 Half-life Method
Zero order: t₁/₂ = [A]₀/2k
First order: t₁/₂ = 0.693/k (independent of concentration)
Second order: t₁/₂ = 1/k[A]₀
6. Temperature Dependence - Arrhenius Equation
Arrhenius Equation: k = Ae^(-Ea/RT)
Logarithmic Form: ln k = ln A - Ea/RT
Where:
A = pre-exponential factor (frequency factor)
Ea = activation energy (J/mol)
R = gas constant (8.314 J mol⁻¹ K⁻¹)
T = absolute temperature (K)
Two-Temperature Form: ln(k₂/k₁) = (Ea/R)(1/T₁ - 1/T₂)
7. Collision Theory
Postulates:
1. Molecules must collide to react
2. Only collisions with energy ≥ Ea are effective
3. Molecules must have proper orientation
Rate Equation: Rate = ZPₑPₛ
Where:
Z = collision frequency
Pₑ = fraction of collisions with sufficient energy
Pₛ = steric factor (proper orientation)
8. Reaction Mechanisms
Elementary Reactions: Single-step reactions
Molecularity = number of molecules participating
Rate law can be written directly from stoichiometry
Complex Reactions: Multi-step reactions
Overall rate determined by rate-determining step
Intermediates are formed and consumed
Types:
Consecutive reactions: A → B → C
Parallel reactions: A → B and A → C
Chain reactions: Initiation → Propagation → Termination
9. Steady-State Approximation
For intermediate species: d[intermediate]/dt ≈ 0
Used to derive rate laws for complex mechanisms when intermediates are consumed as quickly as
they're formed.
10. Catalysis
10.1 Homogeneous Catalysis
Catalyst in same phase as reactants
Often involves intermediate formation
10.2 Heterogeneous Catalysis
Catalyst in different phase (usually solid)
Involves adsorption, reaction, and desorption
10.3 Enzyme Catalysis
Michaelis-Menten equation: v = (Vₘₐₓ[S])/(Kₘ + [S])
Highly specific and efficient biological catalysts
11. Important Graphs and Plots
11.1 Concentration vs Time
Zero order: linear decrease
First order: exponential decay
Second order: hyperbolic decrease
11.2 Linearization Plots
Zero order: [A] vs t (straight line)
First order: ln[A] vs t (straight line)
Second order: 1/[A] vs t (straight line)
11.3 Arrhenius Plot
ln k vs 1/T gives straight line
Slope = -Ea/R
Intercept = ln A
12. Key Formulas Summary
Order Rate Law Integrated Form Half-life Units of k
0 Rate = k [A] = [A]₀ - kt [A]₀/2k mol L⁻¹ s⁻¹
1 Rate = k[A] ln[A] = ln[A]₀ - kt 0.693/k s⁻¹
2 Rate = k[A]² 1/[A] = 1/[A]₀ + kt 1/k[A]₀ L mol⁻¹ s⁻¹
13. Problem-Solving Tips
1. Identify the order: Use initial rate data or integrated rate law plots
2. Calculate rate constant: Use appropriate integrated rate equation
3. Find activation energy: Use Arrhenius equation with two temperatures
4. Determine mechanism: Identify elementary steps and rate-determining step
5. Half-life problems: Use appropriate half-life formula based on order
14. Common Mistakes to Avoid
Confusing reaction order with stoichiometric coefficients
Using wrong units for rate constant
Forgetting temperature must be in Kelvin for Arrhenius equation
Mixing up reactant vs product concentrations in rate expressions
Not considering that catalysts don't appear in overall rate law
