The rate constant for the decomposition of N2O5 at various temperatures is given below:
| T/°C | 0 | 20 | 40 | 60 | 80 |
|---|---|---|---|---|---|
| 105×k/s−1 | 0.0787 | 1.70 | 25.7 | 178 | 2140 |
Draw a graph between lnk and 1/T and calculate the values of A and Ea. Predict the rate constant at 30° and 50°C.
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Arrhenius Equation
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 in its linear form:
lnk=lnA−REa⋅T1.
A plot of lnk vs 1/T gives a straight line with slope =−Ea/R and intercept =lnA.
Step 1 – Convert data
Convert T to Kelvin: T/K=t/°C+273.15. The given k values are 105×k, so the actual k used for lnk is the table value ×10−5.
| T/°C | T/K | 103/T (K−1) | actual k (s−1) | lnk |
|---|---|---|---|---|
| 0 | 273.15 | 3.661 | 7.87×10−7 | −14.055 |
| 20 | 293.15 | 3.411 | 1.70×10−5 | −10.982 |
| 40 | 313.15 | 3.193 | 2.57×10−4 | −8.266 |
| 60 | 333.15 | 3.002 | 1.78×10−3 | −6.331 |
| 80 | 353.15 | 2.832 | 2.14×10−2 | −3.844 |
Step 2 – Plot and find slope
Plot lnk (y-axis) vs 103/T (x-axis). Using the first and last points:
Slope =(2.832−3.661)×10−3(−3.844)−(−14.055)=−0.829×10−310.211≈−1.232×104 K.
Step 3 – Calculate Ea and A
Ea=−slope×R=1.232×104×8.314≈1.024×105 J/mol = 102.4 kJ/mol.
Intercept lnA=lnk+REa⋅T1. Using the (central) point at 40°C:
lnA=−8.266+(1.232×104)(3.193×10−3)=−8.266+39.34=31.07
A=e31.07≈3.1×1013 s−1. …
Using the Arrhenius equation lnk=lnA−REa⋅T1, we plot lnk vs 1/T to get a straight line. From its slope (−Ea/R) and intercept (lnA), we find Ea≈102.4 kJ mol−1 and A≈3.1×1013 s−1. Then we predict k30∘C≈7.0×10−5 s−1 and k50∘C≈8.6×10−4 s−1.
The Arrhenius equation is the backbone of temperature-dependent kinetics. It tells us that the rate constant k depends exponentially on temperature:
k=Ae−Ea/RT
Taking natural logs gives a linear form:
lnk=lnA−REa⋅T1
This is of the form y=mx+c, where y=lnk, x=1/T, slope m=−Ea/R, and intercept c=lnA. So if we plot lnk against 1/T, we get a straight line — and from its slope and intercept we can extract both Ea and A.
Temperature must be in kelvin when using 1/T in the Arrhenius plot. A common mistake is to use Celsius directly — that gives a completely wrong slope.
Let’s work through it step by step.
1. Convert temperatures to kelvin and compute 1/T and lnk
| T (°C) | T (K) | 1/T (K−1) | k (s−1) | lnk |
|---|---|---|---|---|
| 0 | 273.15 | 3.661×10−3 | 0.0787×10−5 | −14.055 |
| 20 | 293.15 | 3.411×10−3 | 1.70×10−5 | −10.982 |
| 40 | 313.15 | 3.193×10−3 | 25.7×10−5 | −8.266 |
| 60 | 333.15 | 3.002×10−3 | 178×10−5 | −6.331 |
| 80 | 353.15 | 2.832×10−3 | 2140×10−5 | −3.844 |
Notice that k values are given as 105×k, so we divide by 105 to get actual k in s−1.
2. Plot lnk vs 1/T
On a graph, the points fall beautifully on a straight line. The slope is negative (since k increases with T, lnk increases as 1/T decreases). We can calculate the slope using any two well-separated points, but for accuracy, use the first and last:
slope=Δ(1/T)Δ(lnk)=(2.832−3.661)×10−3(−3.844)−(−14.055)=−0.829×10−310.211≈−1.232×104 K
Using the two extreme points gives a quick estimate. For exam problems, this is usually sufficient — but if you have time, a least-squares fit (or averaging slopes from multiple pairs) gives a more reliable result.
3. Calculate Ea from the slope
Since slope =−Ea/R, we have:
−REa=−1.232×104 K
Ea=1.232×104×R=1.232×104×8.314 J mol−1
Ea≈1.024×105 J mol−1=102.4 kJ mol−1
4. Calculate A from the intercept
The intercept c=lnA. From the graph, the line crosses the lnk axis at 1/T=0 (theoretical). Using the point-slope form with any data point, say at T=40∘C:
lnA=lnk+REa⋅T1
lnA=−8.266+(1.232×104)×(3.193×10−3)
lnA=−8.266+39.34=31.07
So:
A=e31.07≈3.1×1013 s−1 …
Method: Graphical Arrhenius Analysis (Two-Point & Linear Regression)
The Arrhenius equation in logarithmic form is:
lnk=lnA−REa⋅T1
This is a straight line: y=mx+c, where:
- y=lnk
- x=1/T (in Kelvin)
- Slope m=−Ea/R
- Intercept c=lnA
Step 1: Convert temperatures to Kelvin and compute 1/T and lnk
The given k values in the table are 105×k, so the actual k used to compute lnk is the table value ×10−5.
| T (°C) | T (K) | 1/T (K−1) | k×105 (s−1) | actual k (s−1) | lnk |
|---|---|---|---|---|---|
| 0 | 273.15 | 3.661×10−3 | 0.0787 | 7.87×10−7 | −14.055 |
| 20 | 293.15 | 3.411×10−3 | 1.70 | 1.70×10−5 | −10.982 |
| 40 | 313.15 | 3.193×10−3 | 25.7 | 2.57×10−4 | −8.266 |
| 60 | 333.15 | 3.002×10−3 | 178 | 1.78×10−3 | −6.331 |
| 80 | 353.15 | 2.832×10−3 | 2140 | 2.14×10−2 | −3.844 |
Step 2: Plot lnk (y-axis) vs 1/T (x-axis)
You will get a straight line with a negative slope.
Step 3: Calculate slope from the graph
Using the first and last points (for a quick estimate):
slope=Δ(1/T)Δlnk=(2.832−3.661)×10−3−3.844−(−14.055)
=−0.829×10−310.211≈−1.232×104 K
Step 4: Calculate activation energy Ea
From slope m=−Ea/R:
Ea=−m×R=1.232×104×8.314
Ea≈1.024×105 J/mol=102.4 kJ/mol
Step 5: Calculate pre-exponential factor A
From intercept c=lnA:
Using the central point at T=313.15 K (1/T=3.193×10−3, lnk=−8.266):
lnA=lnk+REa⋅T1
lnA=−8.266+(1.232×104)(3.193×10−3)
lnA=−8.266+39.34=31.07
A=e31.07≈3.1×1013 s−1
Step 6: Predict rate constants at 30°C and 50°C
Use the fitted line lnk=31.07−T1.232×104.
At 30°C (303.15 K):
lnk=31.07−(1.232×104)(3.299×10−3) …
Common Mistakes & How to Avoid Them (Arrhenius Equation)
1. ✗ Forgetting to convert temperature to Kelvin
The Mistake: Students plot 1/T using °C values directly (e.g., 1/20 instead of 1/293).
Why it's wrong: The Arrhenius equation uses absolute temperature:
k=Ae−Ea/RT
T must be in Kelvin (K=°C+273).
✓ How to avoid: Always write the conversion step explicitly:
- 0°C=273K
- 20°C=293K
- 40°C=313K, etc.
2. ✗ Using k directly instead of lnk
The Mistake: Plotting k vs 1/T (a curve) instead of lnk vs 1/T (a straight line).
Why it's wrong: The Arrhenius equation in linear form is:
lnk=lnA−REa⋅T1
Only lnk vs 1/T gives a straight line with slope =−Ea/R.
✓ How to avoid: Before plotting, compute lnk for each k value. Use a table:
| T/K | 105k | lnk | 1/T |
|---|---|---|---|
| 273 | 0.0787 | ln(0.0787×10−5) | 0.00366 |
| ... | ... | ... | ... |
3. ✗ Mishandling the 105 factor in k
The Mistake: Taking ln(0.0787) instead of ln(0.0787×10−5).
Why it's wrong: The given k values are 105×k. So actual k=(table value)×10−5.
✓ How to avoid: Write clearly:
kactual=(table value)×10−5
Then take ln of this actual value.
4. ✗ Using R in wrong units
The Mistake: Using R=0.0821 (L·atm/mol·K) instead of R=8.314 (J/mol·K).
Why it's wrong: Ea is typically in J/mol or kJ/mol. The correct R for energy calculations is:
R=8.314 J mol−1K−1
✓ How to avoid: Remember:
- For Ea in J/mol: use R=8.314
- For Ea in kJ/mol: use R=0.008314
5. ✗ Confusing slope sign when finding Ea
The Mistake: Taking Ea=slope×R instead of Ea=−slope×R.
Why it's wrong: From lnk=lnA−REa⋅T1, the slope is negative:
slope=−REa
So Ea=−slope×R (which gives a positive value).
✓ How to avoid:
- Plot the graph
- Calculate slope =Δ(1/T)Δlnk (will be negative)
- Then Ea=−slope×R
6. ✗ Using wrong points for interpolation at 30°C and 50°C
The Mistake: Reading k directly from the curved k vs T plot.
Why it's wrong: The relationship is linear only for lnk vs 1/T. …
Showing the 12 most recent of 15 on this concept.
- COMEDK 2026Set 2026-A1 markMCQQ.A first order reaction is 50% complete in 30 minutes at 300 K and in 10 minutes at 320 K . The activation energy of the reaction ( Ea ) is: [R=8.314 J K−1 mol−1;log2=0.3010;log3=0.4771] (A) 75.2 kJ mol−1 (B) 43.8 kJ mol−1 (C) 23.7 kJ mol−1 (D) 52.5 kJ mol−1
›Reveal solutionSolution
For a first‑order reaction, the half‑life is inversely proportional to the rate constant. Using the two half‑lives at different temperatures in the Arrhenius equation gives the activation energy. The result is approximately 43.8 kJ mol⁻¹, which corresponds to option (B).
Concept & Intuition
For a first‑order reaction, the half‑life t1/2 is related to the rate constant k by
t1/2=kln2.
Thus, k∝1/t1/2. When temperature changes, the rate constant changes according to the Arrhenius equation:
lnk1k2=REa(T11−T21).
Since k∝1/t1/2, we can replace the ratio of rate constants by the inverse ratio of half‑lives. This lets us find Ea directly from the given half‑life data.
Step‑by‑step solution
- Write the half‑life relation for a first‑order reaction
t1/2=kln2⇒k=t1/2ln2.
So at temperature T1=300 K, t1/2(1)=30 min; at T2=320 K, t1/2(2)=10 min.
- Form the ratio of rate constants
k1k2=ln2/t1/2(1)ln2/t1/2(2)=t1/2(2)t1/2(1)=1030=3.
- Apply the Arrhenius equation in logarithmic form
lnk1k2=REa(T11−T21).
Substitute k1k2=3 and R=8.314 J K−1mol−1:
ln3=8.314Ea(3001−3201).
- Compute the temperature difference term
3001−3201=300×320320−300=9600020=48001.
So
ln3=8.314Ea×48001.
- Solve for Ea
Ea=8.314×4800×ln3.
Use ln3=2.3026×log103 (since lnx=2.3026log10x). Given log3=0.4771, …
- COMEDK 2026Set 2026-M1 markMCQQ.The rate constants for two different reactions, k1 and k2 are 1016⋅e−2000/T and 1015⋅e−1000/T respectively. The temperature at which k1=k2 is (A) 1000K (B) 2.3032000K (C) 2.3031000K (D) 2000K
›Reveal solutionSolution
The key idea is to set the two Arrhenius‑type rate constants equal and solve for temperature. The result is T=2.3031000 K, which corresponds to option (C).
We are given two rate constants of the Arrhenius form:
k1=1016e−2000/T and k2=1015e−1000/T.
The problem asks for the temperature at which they are equal.
The natural approach is to set k1=k2 and solve for T. Because the expressions involve exponentials, we will use logarithms to bring the exponents down.
- Set the two expressions equal
1016e−2000/T=1015e−1000/T
- Divide both sides by 1015 to simplify the pre‑exponential factors:
10151016e−2000/T=e−1000/T
10e−2000/T=e−1000/T
- Take the natural logarithm of both sides
ln(10)+ln(e−2000/T)=ln(e−1000/T)
Since ln(eu)=u, this becomes:
ln(10)−T2000=−T1000
- Collect the terms with T Add T2000 to both sides:
ln(10)=T2000−T1000
ln(10)=T1000
- Solve for T
T=ln(10)1000
Now recall that ln(10)≈2.302585, so we can write:
T=2.3031000 K …
- COMEDK 2025Set 2025-A1 markMCQQ.The hydrogenation of Ethyne is carried out at 600 K . The same reaction when carried out in presence of a catalyst maintaining the same rate constant, the temperature required is only 400 K . If the catalyst lowers the Activation energy of the reaction by 20 kJ/mol, what is the value of Ea ? (A) 60 kJ/mol (B) 100 kJ/mol (C) 50 kJ/mol (D) 80 kJ/mol
›Reveal solutionSolution
The key idea is that the catalyst keeps the rate constant the same at a lower temperature by reducing the activation energy. Using the Arrhenius equation in logarithmic form, we equate the rate constants at the two different conditions and solve for the original activation energy, which comes out to be 60 kJ/mol.
Concept and Intuition
The Arrhenius equation tells us that the rate constant k depends on both the activation energy Ea and the temperature T:
k=Ae−Ea/(RT)
If a catalyst lowers Ea by ΔE, the reaction can proceed at the same rate (same k) at a lower temperature. Here, the uncatalyzed reaction at 600 K has the same rate constant as the catalyzed reaction at 400 K, with the catalyst reducing Ea by 20 kJ/mol. We set the two Arrhenius expressions equal and solve for the original Ea.
Step-by-step solution
- Write the Arrhenius equation for both cases. For the uncatalyzed reaction at T1=600 K:
k=Ae−Ea/(RT1)
For the catalyzed reaction at T2=400 K, the activation energy is Ea−20 (in kJ/mol):
k=Ae−(Ea−20)/(RT2)
The pre-exponential factor A is assumed unchanged by the catalyst.
- Equate the two expressions for k. Since the rate constant is the same:
Ae−Ea/(RT1)=Ae−(Ea−20)/(RT2)
Cancel A (non-zero) and take natural logs:
−RT1Ea=−RT2Ea−20
Multiply both sides by −R:
T1Ea=T2Ea−20
- Substitute the temperatures (in Kelvin).
- COMEDK 2025Set 2025-A1 markMCQQ.(i) and(ii) are 2 chemical reactions carried out at TK. (i). X→Y+W with k1 as rate constant. (ii). X→Z+W with k2 as rate constant. The Activation energy for reaction(ii) is 3 times that of reaction (i). What is the expression for k1 ? (A) k1=−2k2e2Ea1/RT (B) k1=k2e2Ea1/RT (C) k1=2k2eEa1/RT (D) k1=k2/2e−Ea1/RT
›Reveal solutionSolution
The problem gives two parallel reactions from the same reactant X, with activation energies related by Ea2=3Ea1. Using the Arrhenius equation and the fact that the pre-exponential factors are equal (same reactant, similar reactions), we find k1=k2e2Ea1/RT, which corresponds to option (B).
The key idea here is the Arrhenius equation, which relates the rate constant k to the activation energy Ea and temperature T:
k=Ae−Ea/RT
where A is the pre-exponential factor (frequency factor). For two reactions starting from the same reactant and producing similar products, it is reasonable to assume the pre-exponential factors are equal: A1=A2. The problem gives Ea2=3Ea1. We can then write expressions for k1 and k2 and eliminate the common A to relate them.
- Write the Arrhenius equations for both reactions For reaction (i): k1=A1e−Ea1/RT For reaction (ii): k2=A2e−Ea2/RT Given Ea2=3Ea1 and assuming A1=A2=A, we have:
k1=Ae−Ea1/RT,k2=Ae−3Ea1/RT
- Divide the two equations to eliminate A
k2k1=Ae−3Ea1/RTAe−Ea1/RT=e(−Ea1+3Ea1)/RT=e2Ea1/RT
- Solve for k1 Multiply both sides by k2: k1=k2e2Ea1/RT …
- COMEDK 2025Set 2025-E1 markMCQQ.When the temperature of a reaction A+B→C is increased from 300 K to 310 K the rate constant increases by 12%. What is the Activation energy of the reaction? (A) 163.9 kJ/mol (B) 85.69 kJ/mol (C) 192.17 kJ/mol (D) 8.76 kJ/mol
›Reveal solutionSolution
From the Arrhenius equation with k2/k1=1.12 between 300 K and 310 K, Ea≈8.76 kJ/mol — option (D).
A 12% increase means k1k2=1.12. The two-temperature Arrhenius form:
lnk1k2=REa(T11−T21).
T11−T21=3001−3101=9300010=1.075×10−4 K−1,
ln(1.12)=0.1133.
Solving for Ea (with R=8.314 J mol−1K−1): …
- COMEDK 2025Set 2025-M1 markMCQQ.Two statements, One Assertion (A) and the other Reason (R) are given. Choose the right option. Assertion: The rate constant (k) for a chemical reaction gets nearly doubled for a 100 rise in temperature. Reason: The number of bimolecular collisions between reactant molecules increase with increase in temperature (A) A is correct but R is wrong. (B) Both A and R are correct but R is not the correct explanation of A . (C) Both A and R are correct and R is the correct explanation of A. (D) A is wrong but R is correct.
›Reveal solutionSolution
The assertion that the rate constant roughly doubles for a 10 °C rise is empirically true for many reactions near room temperature, but the reason given — increased bimolecular collision frequency — is not the correct explanation; the real cause is the exponential increase in the fraction of molecules with energy above the activation barrier.
The key concept here is the Arrhenius equation, which separates the effect of temperature on reaction rates into two parts: the collision frequency and the fraction of collisions that are energetic enough to overcome the activation energy. While both factors increase with temperature, the dominant effect for a typical 10 °C rise is the exponential increase in the fraction of high-energy molecules, not the modest increase in collision frequency.
- Understanding the Assertion (A) The statement that the rate constant k nearly doubles for a 10 °C rise is a well-known rule of thumb for many reactions near room temperature. This comes from the Arrhenius equation:
k=Ae−Ea/(RT)
where A is the pre-exponential factor (related to collision frequency and orientation), Ea is the activation energy, R is the gas constant, and T is the absolute temperature.
For a typical activation energy of about 50 kJ/mol, a 10 °C rise from 300 K to 310 K gives:
k300k310=exp[−REa(3101−3001)]≈exp(8.31450000×300×31010)≈e0.65≈1.92
So the assertion is correct for many common reactions.
- Understanding the Reason (R) The reason states that the number of bimolecular collisions between reactant molecules increases with temperature. This is true — from kinetic molecular theory, the collision frequency is proportional to T. For a 10 °C rise from 300 K to 310 K, the increase is:
300310≈1.016
That’s only about a 1.6% increase, far from the ~100% increase in the rate constant. So while the reason is factually correct, it is not sufficient to explain the near-doubling of k.
- Why the reason fails as an explanation …
- COMEDK 2025Set 2025-M1 markMCQQ.Two chemical reactions of the same order have equal Frequency factor value. Their Activation energies differ by 26.8 kJ/mol. At 300 K if k2=xk1 find the value of x. (A) 4.631×104 (B) 1.143×103 (C) 2.286×103 (D) 4.665
›Reveal solutionSolution
The ratio of rate constants for two reactions with equal frequency factors depends only on the difference in activation energies via the Arrhenius equation. Using ΔEa=26.8 kJ/mol at T=300 K, we find x=eΔEa/(RT)≈4.631×104, so option (A) is correct.
The key idea is the Arrhenius equation:
k=Ae−Ea/(RT)
When two reactions have the same frequency factor A, the ratio of their rate constants depends only on the difference in activation energies. This lets us directly compute x=k2/k1 without needing absolute values.
- Write the Arrhenius expressions For reaction 1: k1=Ae−Ea1/(RT) For reaction 2: k2=Ae−Ea2/(RT) Since A is equal, the ratio is:
k1k2=e−(Ea2−Ea1)/(RT)
- Interpret the given difference The activation energies differ by 26.8 kJ/mol. We are not told which is larger, but the problem states k2=xk1. If Ea2<Ea1, then k2>k1 and x>1. Given the options, x is large, so we take Ea1−Ea2=26.8 kJ/mol (i.e., reaction 2 has the lower activation energy). Thus:
k1k2=e(Ea1−Ea2)/(RT)=eΔEa/(RT)
- Plug in values with consistent units ΔEa=26.8 kJ/mol=26800 J/mol R=8.314 J/(mol⋅K) T=300 K So:
- KCET 2024Set B-21 markMCQQ.Which one of the following does not represent Arrhenius equation? (A) logk=logA−2.303RTEa (B) k=Ae−Ea/RT (C) lnk=−RTEa+lnA (D) k=AeEa/RT
›Reveal solutionSolution
Three options are algebraic rearrangements of k=Ae−Ea/RT; the odd one out has lost the minus sign in the exponent.
Step 1 — The Arrhenius equation.
k=Ae−Ea/RT
The exponential factor e−Ea/RT is the Boltzmann fraction — the fraction of molecular collisions with energy at least Ea. A fraction must be ≤1, which forces the exponent to be negative.
Step 2 — Check each option.
(B) k=Ae−Ea/RT — this is the Arrhenius equation. ✓ (represents it)
(C) Take ln of (B):
lnk=lnA+ln(e−Ea/RT)=lnA−RTEa=−RTEa+lnA.✓
(A) Convert (C) to base-10 using lny=2.303logy:
2.303logk=2.303logA−RTEa⇒logk=logA−2.303RTEa.✓
(D) k=Ae+Ea/RT — the sign is flipped. ✗ …
- COMEDK 2024Set 2024-E1 markMCQQ.In the presence of a catalyst at a given temperature of 27∘C, the Activation energy of a specific reaction is reduced by 100 J/mol. What is the ratio between the rate constants for the catalysed (k2) and uncatalysed (k1) reactions? (A) 1.04×10−2 (B) 2.32×10−2 (C) 1.97 (D) 1.04
›Reveal solutionSolution
Lowering Ea by 100 J/mol at 300 K raises the rate constant by a factor e100/RT=e0.0401≈1.04.
From the Arrhenius equation, at the same temperature:
k1k2=Ae−Ea1/RTAe−Ea2/RT=e(Ea1−Ea2)/RT=eΔEa/RT …
- COMEDK 2024Set 2024-E1 markMCQQ.The Activation energy for the reaction A→B+C, at a temperature TK was 0.04606 RT J/mol. What is the ratio of Arrhenius factor to the Rate constant for this reaction? (A) 1.585 (B) 3.2×10−2 (C) 1.047×10−2 (D) 1.047
›Reveal solutionSolution
A/k=eEa/RT=e0.04606≈1.047.
Arrhenius equation: k=Ae−Ea/RT, so
kA=eEa/RT
Here Ea=0.04606RT, hence Ea/RT=0.04606. …
- COMEDK 2024Set 2024-M1 markMCQQ.The rate constant for the reaction A→B+C at 500 K is given as 0.004 s−1. At what temperature will the rate constant become 0.014 s−1 ? Ea for the reaction is 18.231 kJ. (A) 950 K (B) 597 K (C) 700 K (D) 800 K
›Reveal solutionSolution
Apply the two-temperature Arrhenius equation with k1=0.004s−1 at 500K and k2=0.014s−1; solving gives T2≈700K.
lnk1k2=REa(T11−T21)
With Ea=18231J mol−1, R=8.314J mol−1K−1:
ln0.0040.014=ln(3.5)=1.253,REa=8.31418231=2193. …
- KCET 2023Set D-21 markMCQQ.At 500 K, for a reversible reaction A2(g)+B2(g)⇌2AB(g) in a closed container, Kc=2×10−5. In the presence of catalyst, the equilibrium is attaining 10 times faster. The equilibrium constant Kc in the presence of catalyst at the same temperature is (A) 2×10−4 (B) 2×10−6 (C) 2×10−10 (D) 2×10−5
›Reveal solutionSolution
A catalyst does not change the equilibrium constant — it only speeds up the rate at which equilibrium is reached. So Kc remains 2×10−5 at the same temperature. The correct option is (D).
The key idea here is simple but often misunderstood: a catalyst affects the rate of a reaction, not the position of equilibrium. Let’s see why.
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What a catalyst does
A catalyst provides an alternative reaction pathway with a lower activation energy. This means both the forward and reverse reactions are accelerated equally. Because it speeds up both directions by the same factor, the ratio of the forward rate constant to the reverse rate constant — which is exactly Kc — stays unchanged.
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Equilibrium constant depends only on temperature
For a given reaction, Kc is a function of temperature alone. It is determined by the standard Gibbs free energy change:
ΔG∘=−RTlnKc
A catalyst does not alter ΔG∘; it only lowers the activation barrier. So at the same temperature, Kc is fixed.
- The “10 times faster” detail …
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