Q.All energetically effective collisions do not result in a chemical change. Explain with the help of an example.
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The Arrhenius Equation Plot: Why Temperature Changes Reaction Speed
You already know that heating things up makes reactions go faster. A cold chai takes forever to dissolve sugar; hot chai does it in seconds. But how much faster? And is there a pattern that holds for every reaction?
That pattern is the Arrhenius equation, and plotting it in a clever way reveals something fundamental about how molecules need to collide to react.
The core idea: an energy barrier
Imagine a ball sitting in a valley. To get to the next valley, it must first be pushed up over a hill. That hill is the activation energy (Ea) — the minimum energy two molecules need to have when they collide, for the reaction to happen.
At a low temperature, most molecules move slowly. Only a tiny fraction have enough energy to climb that hill. Raise the temperature, and suddenly many more molecules have the required energy. The fraction of molecules with energy ≥Ea is given by the Boltzmann distribution:
fraction=e−Ea/RT
where R is the gas constant and T is the absolute temperature (in Kelvin). This exponential is the heart of the story.
The Arrhenius equation (precise statement)
The rate constant k of a reaction depends on temperature as:
k=Ae−Ea/RT
- k = rate constant (how fast the reaction proceeds)
- A = pre-exponential factor (frequency of collisions, times a steric factor — how often molecules hit in the right orientation)
- Ea = activation energy (J/mol or kJ/mol)
- R = 8.314 J/(mol·K)
- T = temperature in Kelvin
k is not the reaction rate itself — it's the proportionality constant in the rate law. But for a fixed concentration, a larger k means a faster reaction.
Why plot it? The linear trick
The equation k=Ae−Ea/RT is exponential in 1/T. That's hard to eyeball. But take the natural logarithm of both sides:
lnk=lnA−REa⋅T1
This is the equation of a straight line:
y=c+mx
where:
- y=lnk
- x=1/T
- slope m=−Ea/R
- intercept c=lnA
So if you measure k at several temperatures and plot lnk versus 1/T, you get a straight line — provided the reaction follows Arrhenius behaviour (most do, over moderate temperature ranges).
Always use Kelvin for T. Celsius will give you a curved mess because 1/T is not linear in Celsius.
What the plot tells you
From the slope, you get Ea:
Ea=−(slope)×R
A steep negative slope means a large Ea — the reaction is very sensitive to temperature. A shallow slope means a small Ea — temperature doesn't affect it much.
From the intercept, you get A:
A=eintercept
This tells you about the collision frequency and orientation factor. A high A means molecules are colliding often and in the right geometry.
A typical Arrhenius plot looks like this
| T (K) | k (s⁻¹) | 1/T (K⁻¹) | lnk |
|---|---|---|---|
| 300 | 0.0012 | 0.00333 | -6.72 |
| 310 | 0.0028 | 0.00323 | -5.88 |
| 320 | 0.0061 | 0.00313 | -5.10 |
| 330 | 0.0125 | 0.00303 | -4.38 |
Plot lnk (y-axis) vs 1/T (x-axis). The points fall on a straight line. Draw the best-fit line, measure its slope, and compute Ea. …
Why this formula?
Arrhenius Equation: Why It Holds
The Arrhenius equation is not a guess — it emerges from a deep physical picture of how molecules react. Let's build that picture step by step.
1. The Core Question
Why does reaction rate increase dramatically with temperature?
For many reactions, a 10 °C rise can double or triple the rate. This cannot be explained by simple kinetic energy arguments alone — the relationship is exponential.
2. The Key Insight: An Energy Barrier
Before molecules can react, they must collide — but not all collisions lead to products.
There is a minimum energy threshold called activation energy (Ea). Only collisions with energy ≥ Ea can break old bonds and form new ones.
Think of it like pushing a boulder over a hill:
- The hilltop is the transition state (activated complex).
- Ea is the height of that hill from the reactant valley.
3. The Boltzmann Factor — The "Why" of Exponential Dependence
At temperature T, the fraction of molecules with energy ≥ Ea is given by the Boltzmann distribution:
Fraction=e−Ea/(RT)
where:
- R = universal gas constant (8.314 J mol⁻¹ K⁻¹)
- T = absolute temperature (Kelvin)
Why this form?
- The Boltzmann distribution tells us that the probability of a molecule having energy E is proportional to e−E/(kBT).
- For 1 mole of molecules, kB (Boltzmann constant) becomes R via R=NAkB.
- So the fraction with energy ≥ Ea is the integral of that distribution from Ea to ∞, which yields e−Ea/(RT).
Key takeaway: This exponential factor is not arbitrary — it comes directly from statistical mechanics.
4. The Pre-Exponential Factor (A)
Even if a collision has enough energy, it must also:
- Have the correct orientation (steric factor)
- Occur with sufficient collision frequency
These are bundled into the pre-exponential factor A (also called the frequency factor):
A=(collision frequency)×(orientation factor)
For simple gas-phase reactions, collision frequency can be calculated from kinetic molecular theory — it's on the order of 1010 L mol⁻¹ s⁻¹.
5. Putting It Together: The Arrhenius Equation
The rate constant k is proportional to:
- The number of effective collisions per second (given by A)
- The fraction of collisions with sufficient energy (given by e−Ea/(RT))
Thus:
k=Ae−Ea/(RT)
This is the Arrhenius equation.
6. Why It Works — The Physical Logic
| Component | Physical meaning | Why it's there |
|---|---|---|
| A | Maximum possible rate if every collision worked | Accounts for collision frequency & geometry |
The key idea is the Arrhenius Equation, which separates the total collision frequency from the fraction of collisions that actually overcome the activation energy barrier.
- For a reaction to occur, molecules must collide with sufficient energy (≥ activation energy, Ea) and the correct orientation.
- The Arrhenius equation k=Ae−Ea/RT shows that A (the frequency factor) accounts for both the collision rate and the steric (orientation) requirement. Only a fraction of collisions have the right geometry.
- Even if a collision is energetically effective (has E≥Ea), the molecules may bounce apart without reacting if the reactive sites do not align properly. …
The Arrhenius equation tells us that only a fraction of collisions have enough energy (Ea), but even those must also have the correct orientation to break old bonds and form new ones. For example, in the reaction NOX2+CONO+COX2, a collision where the carbon of CO hits the nitrogen of NO₂ is ineffective — the oxygen must be transferred from NO₂ to CO, so only a head-on collision with the right geometry works.
The idea that every collision between reactant molecules leads to a product is a common oversimplification. In reality, two conditions must be satisfied for a collision to be effective (i.e., to result in a chemical change):
- The colliding molecules must possess sufficient kinetic energy to overcome the activation energy barrier (Ea).
- The molecules must be oriented properly relative to each other so that the necessary bonds can break and form.
The Arrhenius equation captures the energy requirement:
k=Ae−Ea/RT
Here, A (the pre-exponential factor) includes the frequency of collisions and the steric (orientation) factor. Even if Ea is met, a poor orientation means no reaction — the molecules simply bounce apart.
Step-by-step explanation with an example
1. Choose a reaction where orientation matters
Consider the gas-phase reaction between nitrogen dioxide and carbon monoxide:
NOX2(g)+CO(g)NO(g)+COX2(g)
This is a simple bimolecular reaction where an oxygen atom is transferred from NO₂ to CO.
2. What must happen at the molecular level?
For the reaction to occur, the oxygen atom bonded to nitrogen in NO₂ must come into contact with the carbon atom in CO. The collision must be head-on — the carbon end of CO must strike the oxygen end of NO₂.
3. An ineffective collision — despite enough energy …
Concept: The Activation Energy Barrier & Effective Collision Theory
The idea that not all energetically effective collisions lead to a reaction is rooted in the Collision Theory and the concept of the Activation Energy (Ea).
Method: The "Orientation & Energy" Filter Method
This method explains why a collision can have enough kinetic energy but still fail to produce products.
Step 1: Check the Energy Condition
- For a reaction to occur, colliding molecules must possess total kinetic energy ≥ Activation Energy (Ea).
- This is the "energetically effective" part — the collision has enough energy to break existing bonds.
Step 2: Check the Orientation Condition
- Even if the energy condition is met, the molecules must collide in the correct geometric orientation.
- The reactive sites (atoms or groups) must face each other properly for bond formation to begin.
Step 3: Apply the Filter
- If Step 1 passes but Step 2 fails → No reaction occurs.
- Only collisions that pass both filters are effective collisions leading to chemical change.
Example: Reaction between NO and O3
Consider the reaction:
NO(g)+O3(g)→NO2(g)+O2(g)
Energetically effective collision (high energy):
- Both molecules approach with sufficient speed (high KE). …
Here are the common mistakes students make when answering this question, along with how to avoid each.
Mistake 1: Confusing "Energetically Effective" with "Sufficient Energy"
- The Mistake: Students often think "energetically effective" simply means the colliding molecules have kinetic energy greater than or equal to the activation energy (Ea). They then state that all such collisions should lead to a reaction.
- Why it's Wrong: The definition of an effective collision in collision theory is stricter. It requires two conditions:
- Sufficient kinetic energy (≥ Ea).
- Proper orientation of the molecules at the moment of impact. The phrase "energetically effective" only satisfies condition 1. The question explicitly asks why condition 1 alone is not enough.
- How to Avoid: Always write the two conditions for an effective collision in your notes. When you see "energetically effective," immediately think: "This only covers the energy part. What about the orientation part?"
Mistake 2: Giving a Vague or Incorrect Example
- The Mistake: Providing an example like "sodium and chlorine react" or "burning paper." These are either too simple (ionic reactions where orientation is less critical) or too complex (involving multiple steps).
- Why it's Wrong: The best examples clearly show that a molecule can hit with enough energy but from the wrong side, so no bond forms. A bad example doesn't illustrate the orientation failure.
- How to Avoid: Memorize the classic textbook example:
- Reaction: 2HI→H2+I2
- Explanation: For the reaction to occur, the two HI molecules must collide such that the H-atom of one molecule hits the I-atom of the other molecule. If the two H-atoms (or two I-atoms) collide with high energy, no reaction occurs—they simply bounce off. The energy is sufficient, but the orientation is wrong.
Mistake 3: Forgetting to Mention the "Transition State"
- The Mistake: The answer only says "they don't have the right orientation" without explaining why orientation matters at the molecular level.
- Why it's Wrong: The examiner wants to see that you understand the concept of the activated complex (transition state). The correct orientation is necessary to form this unstable, high-energy intermediate. …
- TG EAPCET 2024Set eng-2024-05-11-FN1 markMCQQ.At what temperature will the RMS velocity of sulphur dioxide molecules at 400 K be the same as the most probable velocity of oxygen molecules? (A) 600 K (B) 200 K (C) 400 K (D) 300 K
›Reveal solutionSolution
Equating vrms(SO2,400K) with vmp(O2,T) gives T=300 K.
vrms=M13RT1,vmp=M22RT2.
With M(SO2)=64, T1=400 K, and M(O2)=32, set the two speeds equal:
M13RT1=M22RT2 …
- TG EAPCET 2021Set ap-2021-08-10-AN1 markMCQQ.The rate constant of a reaction at 25 ∘C is 1×10−3 min−1. If the temperature coefficient of the reaction is 2, the rate constant (min−1) at 15 ∘C is (A) 2×10−3 (B) 2×10−4 (C) 5×10−4 (D) 4×10−3
›Reveal solutionSolution
The temperature coefficient (Q₁₀ = 2) tells us the rate constant halves for every 10 °C drop. From 25 °C to 15 °C is a 10 °C decrease, so the rate constant at 15 °C is half of 1×10−3 min⁻¹, i.e., 5×10−4 min⁻¹.
Concept & Intuition
The temperature coefficient (often denoted Q10) is defined as the factor by which the rate constant increases when the temperature is raised by 10 °C.
Here Q10=2 means:
- Increase temperature by 10 °C → rate constant doubles.
- Decrease temperature by 10 °C → rate constant halves.
We are moving down from 25 °C to 15 °C, a drop of exactly 10 °C. So the rate constant at the lower temperature is simply k15=k25/2.
Step-by-step reasoning
-
Identify the given data
- k25=1×10−3 min⁻¹
- Temperature coefficient Q10=2
- Temperature change: from 25 °C to 15 °C = −10 °C
-
Apply the definition of temperature coefficient
The relationship is:
kTkT+10=Q10
So for a 10 °C decrease:
k25k15=Q101=21
- Calculate the unknown rate constant k15=k25×21=(1×10−3)×21=0.5×10−3=5×10−4 min−1 …
- TG EAPCET 2021Set ap-2021-08-10-FN1 markMCQQ.The rate constant of a reaction at 25∘C is 1×10−3 min−1. If the temperature coefficient of the reaction is 2, the rate constant (min−1) at 15∘C is (A) 2×10−3 (B) 2×10−4 (C) 5×10−4 (D) 4×10−3
›Reveal solutionSolution
The temperature coefficient (Q₁₀ = 2) tells us the rate constant halves for every 10°C drop. Going from 25°C to 15°C is a 10°C decrease, so the rate constant at 15°C is half of the given value: 5×10−4 min−1.
Concept & Intuition
The temperature coefficient (often denoted Q10) is the factor by which the rate constant changes when the temperature is raised by 10°C. Here Q10=2 means that for every 10°C increase, the rate constant doubles; conversely, for every 10°C decrease, it halves. Since we are moving from 25°C down to 15°C (a drop of exactly 10°C), we simply divide the given rate constant by 2.
Step-by-step reasoning
-
Identify the temperature change
The given rate constant k25=1×10−3 min−1 is at 25∘C. We need k15 at 15∘C.
The difference: 25∘C−15∘C=10∘C.
-
Apply the definition of the temperature coefficient
The temperature coefficient Q10 is defined as
Q10=kTkT+10
Here Q10=2, so for a 10°C increase the rate constant multiplies by 2. For a 10°C decrease, we use the reciprocal:
-
- TG EAPCET 2021Set eng-2021-08-05-AN1 markMCQQ.When salt is added to water, which of the following statement is true? (A) Boiling point decreases (B) Boiling point increases (C) Boiling point remain constant (D) Freezing point increases
›Reveal solutionSolution
Adding salt to water raises its boiling point and lowers its freezing point — a colligative effect. The correct statement is that the boiling point increases.
The question tests your understanding of colligative properties — properties that depend only on the number of solute particles, not their chemical identity. When salt (sodium chloride, NaCl) dissolves in water, it dissociates into Na⁺ and Cl⁻ ions, increasing the total number of particles in the solution. This changes two key physical properties of water: its boiling point and its freezing point.
Why does this happen? At the boiling point, the vapour pressure of the liquid equals the atmospheric pressure. Adding a non-volatile solute like salt lowers the vapour pressure of the solvent (water). To make the vapour pressure reach atmospheric pressure again, you need to supply more heat — hence the boiling point rises. For freezing, the solute particles disrupt the orderly arrangement of water molecules into ice, so a lower temperature is needed to freeze the solution — hence the freezing point drops.
Let’s examine each option step by step.
-
Boiling point behaviour
The boiling point elevation is given by ΔTb=i⋅Kb⋅m, where i is the van’t Hoff factor (for NaCl, i≈2), Kb is the ebullioscopic constant of water, and m is the molality. Since ΔTb>0, the boiling point increases. This eliminates option (A) and (C).
-
Freezing point behaviour …
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