Q.The decomposition of A into product has value of k as 4.5×103 s−1 at 10°C and energy of activation 60 kJ mol−1. At what temperature would k be 1.5×104 s−1?
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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 |
Concept: Arrhenius Equation — the temperature dependence of the rate constant is given by
logk1k2=2.303REa(T11−T21).
Step 1: Identify the known values
k1=4.5×103 s−1, T1=10∘C=283 K
k2=1.5×104 s−1, Ea=60 kJ mol−1=60000 J mol−1
R=8.314 J mol−1K−1
Step 2: Compute the ratio and plug into the equation
k1k2=4.5×1031.5×104=310≈3.333
log(3.333)≈0.5229
Step 3: Solve for T2
0.5229=2.303×8.31460000(2831−T21)
19.14760000≈3133.6 …
Using the Arrhenius equation in its two-point form, the temperature at which the rate constant rises to 1.5×104 s−1 is approximately 297 K (or 24∘C).
The key to this problem is the Arrhenius equation, which tells us how the rate constant k depends on temperature and activation energy. The equation is:
k=Ae−Ea/RT
where A is the pre-exponential factor, Ea is the activation energy, R is the gas constant, and T is the absolute temperature. When we have two different temperatures and their corresponding rate constants, we can eliminate A by taking a ratio. This gives the very useful two-point form:
lnk1k2=REa(T11−T21)
This is the formula we'll use. Notice the order: k2 is the rate constant at the unknown temperature T2, and k1 is the known rate constant at T1. The activation energy must be in the same energy units as R, so we'll use R=8.314 J mol−1K−1 and convert Ea from kJ to J.
Let's work through it step by step.
-
Convert all data to consistent units.
The activation energy is 60 kJ mol−1=60000 J mol−1.
The first temperature is 10∘C=283 K (since T(K)=T(∘C)+273).
The first rate constant is k1=4.5×103 s−1.
The second rate constant is k2=1.5×104 s−1.
We need to find T2.
-
Write the two-point Arrhenius equation with the known values.
ln(4.5×1031.5×104)=8.31460000(2831−T21)
- Simplify the left-hand side.
4.5×1031.5×104=4.515=310≈3.333
So ln(3.333)≈1.204 (using a calculator or knowing ln(10/3)=ln10−ln3≈2.303−1.099=1.204).
- Simplify the right-hand side constant.
REa=8.31460000≈7217 K
So the equation becomes:
1.204=7217(2831−T21)
- Solve for the bracket. …
Method: Two-Point Form of the Arrhenius Equation
This method is used when you know the rate constant at one temperature and the activation energy, and need to find the temperature at which the rate constant takes another value.
Steps
Step 1: Write the two-point Arrhenius equation
The relation between rate constants at two different temperatures is:
logk1k2=2.303REa(T11−T21)
where:
- k1, k2 = rate constants at temperatures T1, T2 (in Kelvin)
- Ea = activation energy (in J/mol)
- R = 8.314 J mol−1K−1
Step 2: Convert given data to consistent units
- k1=4.5×103 s−1 at T1=10∘C=283 K
- k2=1.5×104 s−1 at T2=?
- Ea=60 kJ mol−1=60000 J mol−1
Step 3: Substitute into the equation
log4.5×1031.5×104=2.303×8.31460000(2831−T21)
Step 4: Simplify the left side
4.5×1031.5×104=4.515=3.333...
So:
log(3.333)≈0.5229
Step 5: Compute the constant factor …
Here are the common mistakes students make when solving this Arrhenius-type problem, along with how to avoid each.
1. Forgetting to Convert Celsius to Kelvin
The Mistake:
Plugging T1=10∘C directly into the Arrhenius equation.
The equation uses absolute temperature (Kelvin), not Celsius.
How to Avoid:
Always convert:
T1=10+273=283 K
Write this step explicitly before substituting.
2. Using the Wrong Form of the Arrhenius Equation
The Mistake:
Using k=Ae−Ea/RT directly without realising you need the two-point form to compare two temperatures.
How to Avoid:
When you have k at two different T, always use:
logk1k2=2.303REa(T11−T21)
This avoids needing the pre-exponential factor A.
3. Mixing Up k1 and k2 (or T1 and T2)
The Mistake:
Assigning k1=1.5×104 and k2=4.5×103, then getting a negative or illogical temperature.
How to Avoid:
Label clearly:
- k1=4.5×103 s−1 at T1=283 K
- k2=1.5×104 s−1 at T2=?
Since k2>k1, T2 must be greater than T1. Check your final answer for sense.
4. Unit Errors in Ea and R
The Mistake:
Using Ea=60 kJ mol−1 but R=8.314 J mol−1K−1 without converting.
How to Avoid:
Convert Ea to J/mol:
Ea=60×103=60000 J mol−1
Then R=8.314 J mol−1K−1 works directly.
5. Arithmetic Errors in the Fraction T11−T21
The Mistake:
Computing 2831−T21 incorrectly, or rounding too early.
How to Avoid:
Keep at least 4–5 decimal places during calculation.
Example: …
- 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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