Class 12 Chemistry Notes, Chapter 3: Chemical Kinetics
1. Why Do We Study Chemical Kinetics?
When a chemical reaction takes place, three important questions arise:
- Can the reaction occur?
- Answered by Thermodynamics.
- How much reaction will occur?
- Answered by Chemical Equilibrium.
- How fast will the reaction occur?
- Answered by Chemical Kinetics.
Example
| Reaction | Speed |
|---|---|
| Explosion of crackers | Very Fast |
| Burning of LPG | Fast |
| Digestion of food | Moderate |
| Rusting of iron | Slow |
| Formation of diamond into graphite | Extremely Slow |
2. Reaction Rate
Definition
The rate of a chemical reaction is the change in concentration of reactants or products per unit time.
Simply,
Rate = Change in concentration ÷ Time taken
Two Ways to Express Rate
(A) Rate of Disappearance of Reactant
Since the concentration of reactants decreases with time,Rate=−ΔtΔ[R]
The negative sign makes the rate positive.
(B) Rate of Formation of Product
Since product concentration increases,Rate=+ΔtΔ[P]
Important Point
Reactant concentration decreases.
Product concentration increases.
Therefore,
- Reactant → Negative sign
- Product → Positive sign
3. Units of Reaction Rate
If concentration is measured in mol L⁻¹ and time in seconds,Unit=molL−1s−1
For gaseous reactions expressed using pressure,Unit=atms−1
4. Average Rate of Reaction
Average rate tells us how much concentration changes during a certain time interval.
Formula:Average Rate=−ΔtΔ[R]
orAverage Rate=+ΔtΔ[P]
Characteristics
✔ Calculated over a finite time interval.
✔ Easy to calculate.
✔ Does not give the exact rate at one particular instant.
5. Instantaneous Rate of Reaction
Sometimes we want to know the reaction rate at one exact moment.
This is called Instantaneous Rate.
Mathematically,Rate=−dtd[R]
orRate=+dtd[P]
Graphical Meaning
- Draw a tangent to the concentration–time curve.
- The slope of the tangent gives the instantaneous rate.
Difference Between Average and Instantaneous Rate
| Average Rate | Instantaneous Rate |
|---|---|
| Calculated over a time interval | Calculated at one instant |
| Uses Δ | Uses d (very small change) |
| Easier to calculate | Found from the tangent to the graph |
| Less accurate for a specific moment | Gives the exact rate at that instant |
6. Rate for Different Stoichiometric Coefficients
For a reaction:aA+bB→cC+dD
Rate is written as−a1dtd[A]=−b1dtd[B]=c1dtd[C]=d1dtd[D]
The stoichiometric coefficients are included so that the calculated rate is the same regardless of which reactant or product is used.
Example
For2HI→H2+I2 Rate=−21dtd[HI]=dtd[H2]=dtd[I2]
7. Factors Affecting Reaction Rate
The rate of a reaction depends on:
- Concentration of reactants
- Temperature
- Pressure (for gases)
- Catalyst
- Nature of reactants
- Surface area (for solids)
The chapter focuses mainly on concentration, temperature, pressure (for gases), and catalysts.
8. Rate Law (Rate Equation)
Experiments show that reaction rate depends on reactant concentrations in a specific way.
General form:Rate=k[A]x[B]y
Where:
- k = Rate constant
- [A], [B] = Concentrations
- x, y = Experimentally determined powers
Important Facts About Rate Law
- It is determined experimentally.
- It cannot usually be predicted from the balanced chemical equation.
- The exponents may or may not equal the stoichiometric coefficients.
Example
Reaction:2NO+O2→2NO2
Experimentally,Rate=k[NO]2[O2]
Here,
- Order with respect to NO = 2
- Order with respect to O₂ = 1
- Overall order = 3
9. Rate Constant (k)
The proportionality constant in the rate equation is called the rate constant.
Characteristics
- Constant for a given reaction at a fixed temperature.
- Independent of reactant concentration.
- Changes if temperature changes.
- Higher k means a faster reaction under the same conditions.
Quick Formula Box
Reaction Rate
−ΔtΔ[R] +ΔtΔ[P]
Instantaneous Rate
−dtd[R]
General Rate Law
Rate=k[A]x[B]y
One-Minute Revision
- Chemical kinetics studies the speed of reactions.
- Rate = change in concentration ÷ time.
- Reactants decrease → use a negative sign.
- Products increase → use a positive sign.
- Average rate is calculated over a time interval.
- Instantaneous rate is measured at a particular instant.
- Rate law is determined experimentally.
- General rate equation: Rate = k[A]^x[B]^y.
- Rate constant k is constant only at a fixed temperature.
10. Order of Reaction
Definition
The order of a reaction is the sum of the powers (exponents) of concentration terms present in the rate law expression.
For a reaction:Rate=k[A]x[B]y
Order of reaction:Order=x+y
Examples
Example 1
Rate=k[A]2[B]
Order:=2+1=3
So, it is a third-order reaction.
Example 2
Rate=k[A]1/2[B]3/2
Order:=21+23=2
Reaction order = 2
Important Points About Order
- Order is found experimentally.
- It may be:
- Zero
- One
- Two
- Fractional
- Even negative in some cases
- It is not always equal to the stoichiometric coefficients of the balanced equation.
11. Molecularity of Reaction
Definition
The number of reacting species (atoms, ions, or molecules) that collide simultaneously in an elementary reaction is called molecularity.
Types of Molecularity
1. Unimolecular Reaction
Only one molecule participates.
Example:NH4NO2→N2+2H2O
Molecularity = 1
2. Bimolecular Reaction
Two reacting species participate.
Example:2HI→H2+I2
Molecularity = 2
3. Termolecular Reaction
Three reacting species participate.
Example:2NO+O2→2NO2
Molecularity = 3
Difference Between Order and Molecularity
| Order of Reaction | Molecularity |
|---|---|
| Determined experimentally | Based on reaction mechanism |
| Applies to elementary and complex reactions | Applies only to elementary reactions |
| Can be zero or fractional | Always a whole number |
| Can be negative | Never negative |
| Gives information about rate dependence | Gives number of molecules involved in elementary step |
12. Rate Constant and Its Units
For:Rate=k[A]x[B]y
where:x+y=n
(n = order of reaction)
The units of rate constant depend on the order of reaction.
Zero Order Reaction
Rate:Rate=k
Units of k:molL−1s−1
First Order Reaction
Rate:Rate=k[A]
Units of k:s−1
Second Order Reaction
Rate:Rate=k[A]2
Units of k:Lmol−1s−1
13. Elementary and Complex Reactions
Elementary Reaction
A reaction that occurs in a single step is called an elementary reaction.
Example:A+B→C
Complex Reaction
A reaction that occurs through multiple elementary steps is called a complex reaction.
The complete sequence of steps is called the mechanism of reaction.
14. Rate Determining Step
In a multi-step reaction, the slowest step controls the overall reaction rate.
This slow step is called the:Rate Determining Step
Example:
A relay race depends on the slowest runner. Similarly, the reaction speed depends on the slowest reaction step.
15. Integrated Rate Equations
The rate law gives the relationship between rate and concentration.
However, measuring instantaneous rate is difficult.
Therefore, the differential rate equation is converted into an integrated rate equation, which relates:
- Concentration
- Time
- Rate constant
A. Zero Order Reaction
Definition
A reaction in which the rate is independent of reactant concentration is called a zero-order reaction.
General reaction:R→P
Rate law:Rate=k[R]0
Since:[R]0=1
Therefore:Rate=k
Integrated Rate Equation
−dtd[R]=k
After integration:[R]=[R]0−kt
Where:
- [R]₀ = initial concentration
- [R] = concentration after time t
- k = rate constant
Rate Constant Formula
k=t[R]0−[R]
Graph
For a zero-order reaction:
Graph of:[R] vs t
is a straight line.
- Slope = -k
- Intercept = [R]₀
Examples of Zero Order Reactions
- Decomposition of ammonia on platinum surface:
2NH3→N2+3H2
- Reactions occurring on catalyst surfaces
B. First Order Reaction
Definition
A reaction whose rate depends on the first power of reactant concentration is called a first-order reaction.
General reaction:R→P
Rate law:Rate=k[R]
Integrated Rate Equation
ln[R][R]0=kt
ork=t2.303log[R][R]0
Exponential Form
[R]=[R]0e−kt
Graph
For first-order reaction:
Graph between:ln[R] and t
gives a straight line.
- Slope = -k
- Intercept = ln[R]₀
Examples of First Order Reactions
1. Decomposition of N₂O₅
N2O5→2NO2+21O2
2. Radioactive decay
226Ra→222Rn+He
Quick Revision Table
| Feature | Zero Order | First Order |
|---|---|---|
| Rate law | Rate = k | Rate = k[R] |
| Order | 0 | 1 |
| Integrated equation | [R]=[R]₀−kt | ln([R]₀/[R])=kt |
| Unit of k | mol L⁻¹ s⁻¹ | s⁻¹ |
| Graph | [R] vs t | ln[R] vs t |
| Half-life | Depends on initial concentration | Independent of initial concentration |
Exam Remember Points ⭐
- Order comes from rate law, not balanced equation.
- Molecularity applies only to elementary reactions.
- Zero-order rate is independent of concentration.
- First-order reactions have constant half-life.
- Unit of rate constant depends on reaction order.
16. Half-Life of a Reaction (t½)
Definition
The half-life of a reaction is the time required for the concentration of a reactant to become half of its initial value.
It is represented by:t1/2
A. Half-Life of Zero Order Reaction
For a zero-order reaction:[R]=[R]0−kt
At half-life:[R]=2[R]0
Substituting:2[R]0=[R]0−kt1/2
Therefore:t1/2=2k[R]0
Important Point
For zero-order reactions:t1/2∝[R]0
The half-life increases when the initial concentration increases.
B. Half-Life of First Order Reaction
For first-order reaction:k=t2.303log[R][R]0
At half-life:[R]=2[R]0
Therefore:t1/2=k0.693
Important Point
For first-order reactions:t1/2 is independent of initial concentration
This means every half-life interval takes the same amount of time.
Example:
If a reaction takes 10 minutes for half completion:
- First half → 10 min
- Next half → 10 min
- Next half → 10 min
Comparison of Half-Life
| Reaction Order | Half-Life Formula | Dependence |
|---|---|---|
| Zero Order | 2k[R]0 | Depends on initial concentration |
| First Order | k0.693 | Independent of initial concentration |
17. Pseudo First Order Reaction
Definition
Some reactions are actually of higher order but behave like first-order reactions because one reactant is present in a very large amount.
Such reactions are called pseudo first-order reactions.
Example: Hydrolysis of Ethyl Acetate
Actual reaction:CH3COOC2H5+H2O→CH3COOH+C2H5OH
Rate law:Rate=k[CH3COOC2H5][H2O]
It is a second-order reaction.
But water is taken in very large excess, so its concentration remains almost constant.
Therefore:Rate=k′[CH3COOC2H5]
Hence, it behaves as a first-order reaction.
Other Example
Inversion of cane sugar:C12H22O11+H2O→Glucose+Fructose
18. Temperature Dependence of Reaction Rate
Most reactions become faster when temperature increases.
Reason:
- Molecules gain more kinetic energy.
- More molecules can cross the activation energy barrier.
- More successful collisions occur.
Arrhenius Equation
The effect of temperature on reaction rate is explained by the Arrhenius equation.k=Ae−Ea/RT
Where:
| Symbol | Meaning |
|---|---|
| k | Rate constant |
| A | Frequency factor |
| Ea | Activation energy |
| R | Gas constant |
| T | Temperature in Kelvin |
19. Activation Energy (Ea)
Definition
The minimum energy required by reactant molecules to form products is called activation energy.
It is the energy needed to form an activated complex.
Activated Complex
During a reaction:
Reactants
↓
Activated Complex
↓
Products
The activated complex is an unstable intermediate state having high energy.
Effect of Temperature on Rate
When temperature increases:
- Molecular kinetic energy increases.
- More molecules have energy greater than activation energy.
- Number of successful collisions increases.
- Reaction rate increases.
Logarithmic Form of Arrhenius Equation
Taking natural logarithm:lnk=−RTEa+lnA
This equation represents a straight line:y=mx+c
For graph:lnk vs T1
- Slope:
−REa
- Intercept:
lnA
20. Collision Theory of Reaction Rates
According to collision theory:
A reaction occurs only when reactant molecules collide effectively.
For a successful collision:
Conditions:
- Molecules must collide.
- Collision must have sufficient energy.
- Molecules must have proper orientation.
Effective Collision
An effective collision produces an activated complex and forms products.
21. Catalyst
Definition
A catalyst is a substance that increases the rate of a reaction without undergoing permanent chemical change.
Example:
Manganese dioxide catalyses decomposition of potassium chlorate:2KClO3→2KCl+3O2
How Does a Catalyst Work?
A catalyst:
- Provides an alternative reaction pathway.
- Lowers activation energy.
- Increases reaction rate.
Important Properties of Catalyst
✔ Does not get permanently consumed.
✔ Does not change Gibbs energy (ΔG) of reaction.
✔ Helps only feasible reactions.
✔ A small amount can catalyse a large amount of reactants.
Complete Chapter Quick Revision Sheet
Chemical Kinetics
Study of:
- Rate of reaction
- Reaction mechanism
Rate
Rate=TimeChange in concentration
Rate Law
Rate=k[A]x[B]y
Order:x+y
Molecularity
Number of species colliding in an elementary step.
Zero Order
[R]=[R]0−kt t1/2=2k[R]0
Unit of k:molL−1s−1
First Order
ln[R][R]0=kt t1/2=k0.693
Unit of k:s−1
Arrhenius Equation
k=Ae−Ea/RT
Higher temperature → Faster reaction
Lower activation energy → Faster reaction
Most Important Board Exam Points ⭐
- Difference between order and molecularity.
- Derivation of zero-order integrated rate equation.
- Derivation of first-order integrated rate equation.
- Half-life formulas.
- Arrhenius equation and activation energy.
- Effect of catalyst on activation energy.
- Pseudo first-order reactions.
- Units of rate constant.
A. Complete Formula Sheet
1. Rate of Reaction
Average Rate
Rate=−ΔtΔ[R]
orRate=ΔtΔ[P]
Instantaneous Rate
Rate=−dtd[R]
2. Rate Law
For:aA+bB→Products Rate=k[A]x[B]y
Where:
- k = rate constant
- x = order with respect to A
- y = order with respect to B
Overall order:Order=x+y
3. Units of Rate Constant
| Order | Unit of k |
|---|---|
| Zero order | mol L⁻¹ s⁻¹ |
| First order | s⁻¹ |
| Second order | L mol⁻¹ s⁻¹ |
4. Zero Order Reaction
Rate Equation
Rate=k
Integrated Rate Equation
[R]=[R]0−kt
Rate Constant
k=t[R]0−[R]
Half-Life
t1/2=2k[R]0
Graph
[R] vs t
Straight line:
- Slope = -k
- Intercept = [R]₀
5. First Order Reaction
Rate Equation
Rate=k[R]
Integrated Rate Equation
k=t2.303log[R][R]0
Half-Life
t1/2=k0.693
Concentration-Time Relation
[R]=[R]0e−kt
Graph
ln[R] vs t
Straight line:
- Slope = -k
- Intercept = ln[R]₀
6. Arrhenius Equation
k=Ae−Ea/RT
Log form:lnk=−RTEa+lnA
Two-temperature equation:logk1k2=2.303REa(T1T2T2−T1)
B. Important Numerical Types
Type 1: Average Rate Calculation
Question
For reaction:R→P
Concentration of R changes from 0.03 M to 0.02 M in 25 minutes.
Find average rate.
Solution
Formula:Rate=−ΔtΔ[R] =−250.02−0.03 =250.01 4×10−4Mmin−1
In seconds:25×60=1500s Rate=15000.01 6.67×10−6Ms−1
Type 2: Finding Order from Rate Law
Given:Rate=k[A]1/2[B]3/2
Order:=21+23 Order=2
Reaction is second order.
Type 3: Zero Order Calculation
Question
A zero-order reaction has:[R]0=0.8M
After 20 seconds:[R]=0.4M
Find rate constant.
Solution
Formula:k=t[R]0−[R] k=200.8−0.4 k=0.02 k=0.02molL−1s−1
Type 4: First Order Rate Constant
Question
A first-order reaction has:
Initial concentration:[R]0=1M
After 100 seconds:[R]=0.25M
Find k.
Solution
Formula:k=t2.303log[R][R]0
Substitute:k=1002.303log0.251 =1002.303log4 log4=0.602 k=0.0138 k=1.38×10−2s−1
Type 5: Half-Life Calculation
First Order Reaction
Given:k=0.005s−1
Formula:t1/2=k0.693 =0.0050.693 138.6s
Type 6: Arrhenius Equation Numerical
Given:k1=0.02s−1 k2=0.07s−1
Temperatures:T1=500K T2=700K
Use:logk1k2=2.303REa(T1T2T2−T1)
Find activation energy.
C. Important Concept Questions
Q1. Why does reaction rate increase with temperature?
Answer:
Increasing temperature increases the kinetic energy of molecules. More molecules acquire energy greater than activation energy, producing more successful collisions and increasing reaction rate.
Q2. Why is molecularity never fractional?
Answer:
Molecularity represents the number of molecules participating in an elementary step. Since molecules cannot be present in fractions, molecularity cannot be fractional.
Q3. Why is order determined experimentally?
Answer:
The balanced chemical equation does not always represent the actual reaction mechanism. Therefore, rate law and order must be found experimentally.
Q4. Why does a catalyst increase reaction rate?
Answer:
A catalyst provides an alternative pathway with lower activation energy, making the reaction faster.
D. Board Exam Important Differences
Order vs Molecularity
| Order | Molecularity |
|---|---|
| Experimental quantity | Theoretical concept |
| Applies to all reactions | Only elementary reactions |
| Can be zero/fractional | Always whole number |
| Obtained from rate law | Obtained from mechanism |
Average Rate vs Instantaneous Rate
| Average Rate | Instantaneous Rate |
|---|---|
| Over a time interval | At a specific time |
| Uses Δ | Uses differential form |
| Less accurate | More accurate |
E. Chapter Mind Map
Chemical Kinetics
|
--------------------------------
| | |
Rate Rate Law Mechanism
| | |
Average/Instant Order Molecularity
| |
Integrated Rate Equations
|
--------------------------
| |
Zero Order First Order
| |
[R]=[R]0-kt ln[R]0/[R]=kt
| |
t1/2=[R]0/2k t1/2=0.693/k