Q.Answer on the basis of the following reaction (species labelled (a)–(d) as printed in the Exemplar):
(a)HO−+(b)CH3CH(Cl)CH2CH3→(c)CH3CH(OH)CH2CH3+(d)Cl−
(2-chlorobutane; in the printed diagram the central carbon of
Which of the following statements are correct about the kinetics of this reaction? (Two or more than two options may be correct.)
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Average Rate Of Reaction
Reaction Rate Stoichiometry – From Intuition to Precision
Imagine you are watching a simple reaction:
2NO2→2NO+O2
As NO₂ disappears, NO appears twice as fast as O₂ appears. Why? Because the balanced equation says: for every 2 molecules of NO₂ that break apart, you get 2 molecules of NO and 1 molecule of O₂. The numbers in front of the species — the stoichiometric coefficients — tell you the relative speeds at which reactants vanish and products appear.
That is the core idea: reaction rate stoichiometry is the relationship between the rates of change of different species in a chemical reaction, dictated by their coefficients in the balanced equation.
The Intuitive Picture
Think of a factory assembly line. The balanced equation is like a recipe:
- 2 units of raw material A → 2 units of product B + 1 unit of byproduct C
If the line runs steadily, every time 2 units of A are consumed, 2 units of B are produced and 1 unit of C is produced. So the rate at which A disappears must be twice the rate at which C appears. The rate at which B appears equals the rate at which A disappears (both have coefficient 2).
The stoichiometric coefficients are not speeds themselves — they are scaling factors that connect the speeds of different species.
The Precise Statement
For a general reaction:
aA+bB→cC+dD
The rate of reaction (often called the rate of the process, r) is defined as:
r=−a1dtd[A]=−b1dtd[B]=c1dtd[C]=d1dtd[D]
Here:
- dtd[X] is the instantaneous rate of change of concentration of species X (in mol L⁻¹ s⁻¹).
- The minus sign is used for reactants (their concentration decreases with time).
- The plus sign is used for products (their concentration increases with time).
- Dividing by the coefficient normalises the rate — so r is the same number for every species.
r=−a1dtd[A]=c1dtd[C]
This single value r is the intrinsic rate of the reaction, independent of which species you measure.
How to Use It (Step by Step)
Suppose you are given:
2H2+O2→2H2O
And you measure that dtd[H2]=−0.040 M/s (negative because H₂ is being consumed).
Step 1: Write the rate relation:
r=−21dtd[H2]=−11dtd[O2]=21dtd[H2O]
Step 2: Plug in the known value:
r=−21(−0.040)=+0.020 M/s
Step 3: Find the rate for O₂:
−dtd[O2]=r⇒dtd[O2]=−0.020 M/s
Step 4: Find the rate for H₂O:
21dtd[H2O]=r⇒dtd[H2O]=2r=0.040 M/s
A quick check: the coefficients tell you the relative rates. Here, H₂ disappears twice as fast as O₂, and H₂O appears at the same rate as H₂ disappears (both coefficient 2). Always verify your numbers match the coefficient ratios.
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Why this formula?
Average Rate of Reaction — Why the Formula Holds
Let’s build this from the ground up. The goal is to understand why the average rate formula looks the way it does — not just memorise it.
1. What does "rate of reaction" mean physically?
A chemical reaction changes the concentration of reactants (decreasing) and products (increasing) over time.
- Rate = how fast this change happens.
- If you measure the change over a finite time interval, you get the average rate.
2. The core idea: change per unit time
For any quantity X that changes from X1 to X2 over time t1 to t2:
Average rate of change of X=ΔtΔX=t2−t1X2−X1
This is just the slope of the straight line connecting the two points on a concentration vs. time graph.
3. Applying this to a reaction
Consider a simple reaction:
A→B
- Reactant A is consumed: [A] decreases.
- Product B is formed: [B] increases.
For reactant A (disappearing):
Average rate=−ΔtΔ[A]
Why the minus sign?
Because Δ[A]=[A]2−[A]1 is negative (concentration drops). The rate itself must be positive (speed is never negative). So we multiply by −1.
For product B (appearing):
Average rate=+ΔtΔ[B]
Here Δ[B] is positive, so no minus sign needed.
4. The general formula for any reaction
For a balanced reaction:
aA+bB→cC+dD
The average rate is defined per mole of reaction — so it’s the same number regardless of which species you track.
We divide each ΔtΔ[species] by its stoichiometric coefficient:
Average rate=−a1ΔtΔ[A]=−b1ΔtΔ[B]=+c1ΔtΔ[C]=+d1ΔtΔ[D]
Why divide by the coefficient?
If 2 moles of A disappear for every 1 mole of C formed, then ΔtΔ[A] is twice as large as ΔtΔ[C]. Dividing by the coefficient normalises them to the same "per mole of reaction" rate.
5. Key exam point: the formula in one line
For any species X with stoichiometric coefficient νX (negative for reactants, positive for products):
Average rate=νX1ΔtΔ[X] …
The key idea is that this reaction — as the printed drawing for the Q.35/36 cluster shows (the product is drawn with its configuration unchanged, ruling out a concerted backside attack) — proceeds by the SN1 mechanism, and SN1 kinetics involve only the substrate in the slow step.
Reasoning:
- The rate-determining step of SN1 is the ionisation of the C–Cl bond of (b) alone: (b)slowcarbocation+Cl−. The nucleophile (a) enters only in the later, fast step.
- Therefore Rate=k[(b)] — the rate depends on the concentration of only (b): statement (i) is correct and (ii) is not. …
The drawn reaction of the Q.35/36 cluster proceeds by SN1 (the printed product keeps the substrate's configuration, which a concerted SN2 attack could never give). SN1 kinetics follow from that: the slow step involves only the substrate, so Rate=k[(b)] and the molecularity is one. The correct options are (i) and (iii).
1. Carry the mechanism over from the drawing
This question shares its reaction — and its printed diagram — with the mechanism question just before it (the Exemplar's Q.35). The drawing shows the product (c) with exactly the same spatial arrangement as the substrate (b): C2H5 on the hashed bond, H on the wedge, and OH in the in-plane position Cl occupied. A concerted SN2 attack must invert the carbon, so the drawn outcome rules SN2 out; the depicted pathway is SN1, through a planar carbocation intermediate. The kinetics question must be answered for that mechanism.
2. Write the two steps and find the rate-determining step
Step 1 (slow):CH3CH(Cl)CH2CH3⟶CH3C+HCH2CH3+Cl−
Step 2 (fast):CH3C+HCH2CH3+OH−⟶CH3CH(OH)CH2CH3
The slow, rate-determining step is the ionisation of the C–Cl bond — and it involves only the substrate (b). The hydroxide ion (a) reacts after the bottleneck, so its concentration does not appear in the rate law.
Rate=k[(b)]
Don't let "OH− is a strong nucleophile" pull you toward a bimolecular rate law here. However strong the nucleophile is, in an SN1 reaction it only captures a carbocation that has already formed — speeding up a step that is not rate-determining changes nothing in the measured rate.
3. Molecularity …
Method: Kinetics from the mechanism (not from the overall equation)
Step 1 – Fix the mechanism from the printed drawing
This question uses the same drawn reaction as the mechanism question before it. The product is drawn with the substrate's arrangement unchanged (C2H5 hashed, H on the wedge, OH taking Cl's in-plane position). A concerted SN2 attack must invert the carbon, so the depicted pathway is SN1 — a planar carbocation intermediate forms first.
Step 2 – Identify the rate-determining step
(b)slowcarbocation+Cl−thencarbocation+OH−fast(c)
Only the substrate (b) participates in the slow step.
Step 3 – Write the rate law
Rate=k[(b)]
The rate is independent of [OH−] — first order overall.
Step 4 – Count the molecularity …
Common Mistakes Students Make on This Question
Mistake 1: Assuming SN2 because a strong nucleophile is present
The mistake: Students see HO− + an alkyl halide and reflexively write bimolecular kinetics — rate depending on both (a) and (b), molecularity two.
Why it's wrong: The printed diagram for this reaction cluster shows the product with its configuration unchanged — the same wedge/hash arrangement as the substrate, with OH simply occupying Cl's in-plane position. A concerted SN2 attack must invert the carbon, so the reaction depicted is SN1. In SN1 the nucleophile enters only after the slow ionisation step, so its concentration never appears in the rate law: Rate=k[(b)].
How to avoid: Decide the mechanism first — from the drawing, not from the reagent alone — and only then write the kinetics.
Mistake 2: Confusing molecularity with the overall stoichiometry
The mistake: The overall equation shows two reactants, so students conclude "molecularity = 2" and tick option (iv).
Why it's wrong: Molecularity is counted for the rate-determining elementary step, not the overall equation. In SN1, the slow step is the ionisation of the substrate alone — one species — so the molecularity is one, even though the overall reaction consumes both (a) and (b).
How to avoid: Always split the mechanism into elementary steps, find the slow one, and count the species in that step only.
Mistake 3: Answering the mechanism and kinetics questions inconsistently
The mistake: Treating this kinetics question in isolation from its companion mechanism question about the same drawn reaction — e.g. calling the mechanism SN1 there but writing second-order kinetics here.
Why it's wrong: The two questions describe one reaction. If the mechanism is SN1 (carbocation intermediate), the kinetics must be unimolecular/first order: (i) and (iii). Mixed answers contradict themselves.
How to avoid: For paired questions on one reaction, fix the mechanism once and derive everything else from it.
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- KCET 2025Set D-41 markMCQQ.In the given graph:
Ea for the reverse reaction will be (A) 125 KJ (B) 215 KJ (C) 90 KJ (D) 305 KJ
›Reveal solutionSolution
On an energy profile the forward and backward barriers are both measured to the same peak, so Ea(reverse)=Ea(forward)−ΔH=215−90=125 kJ.
Step 1 — Read the graph.
From the described energy profile:
- The reactants sit at the lower level.
- The curve rises to a peak (the activated complex / transition state).
- The products sit at a higher level than the reactants — so the reaction is endothermic.
- Ea(forward)=215 kJ — measured from reactants up to the peak.
- ΔH=+90 kJ — measured from reactants up to products.
Step 2 — Set an energy scale.
Put the reactants at zero:
E(reactants)=0 kJ
E(peak)=0+Ea(f)=215 kJ
E(products)=0+ΔH=90 kJ
Step 3 — The reverse activation energy.
Running the reaction backwards, the molecules start at the products and must climb to the same peak (the transition state is common to both directions — this is the principle of microscopic reversibility):
Ea(reverse)=E(peak)−E(products)=215−90=125 kJ
Step 4 — Verify with the general relation.
For any reaction, …
- COMEDK 2024Set 2024-A1 markMCQQ.For the reaction, A+3 B→2C+D, the concentration of A changes from 0.0150 to 0.0125 in 1 minute. The rate of formation of C in mol L−1 s−1 is: (A) 6.32×10−5 (B) 8.32×10−5 (C) 3.26×10−5 (D) 2.5×10−5
›Reveal solutionSolution
Rate of reaction =4.17×10−5, and rate of formation of C is twice this =8.32×10−5 mol L−1s−1. Official key: (B).
Working
For A+3B→2C+D, the rate of reaction is
Rate=−dtd[A]=+21dtd[C]
The change in [A] over 1 minute (=60 s):
−ΔtΔ[A]=600.0150−0.0125=600.0025=4.17×10−5 mol L−1s−1
Since C has a stoichiometric coefficient of 2, its rate of formation is twice the rate of reaction: …
- COMEDK 2024Set 2024-A1 markMCQQ.The rate of appearance of bromine is related to the disappearance of bromide ion in the equation given below is: BrO3−(aq) +5Br−(aq) +6H+→3Br2(l)+3H2O(l) (A) dtd[Br2]=35dtd[Br−] (B) dtd[Br2]=−51dtd[Br−] (C) dtd[Br2]=53dtd[Br−] (D) dtd[Br2]=−53dtd[Br−]
›Reveal solutionSolution
The rate of appearance of a product and the rate of disappearance of a reactant are linked by stoichiometric coefficients, with opposite signs. For the given reaction, the correct relation is dtd[Br2]=−53dtd[Br−], which corresponds to option (D).
The key idea is that for a chemical reaction, the rate can be expressed in terms of any reactant or product, but we must account for stoichiometry and sign conventions. The rate of disappearance of a reactant is negative (its concentration decreases), while the rate of appearance of a product is positive (its concentration increases). To relate them, we divide each rate by its stoichiometric coefficient and set them equal in magnitude, then adjust signs.
Let’s work through it step by step.
- Write the general rate expression. For a reaction aA+bB→cC+dD, the rate is defined as:
Rate=−a1dtd[A]=−b1dtd[B]=c1dtd[C]=d1dtd[D]
The negative signs for reactants ensure the rate is positive (since dtd[reactant] is negative).
- Identify the species and coefficients. In the given reaction:
BrO3−+5Br−+6H+→3Br2+3H2O
We care about Br− (reactant, coefficient 5) and Br2 (product, coefficient 3).
- Set up the equality from the general rate. Using the definition:
−51dtd[Br−]=31dtd[Br2]
The left side has a negative sign because Br− is a reactant; the right side has no negative sign because Br2 is a product.
- Solve for the desired relation. Multiply both sides by 3:
- COMEDK 2024Set 2024-E1 markMCQQ.For a reaction 5X+Y→3Z, the rate of formation of Z is 2.4×10−5 mol L−1 s−1 Calculate the average rate of disappearance of X. (A) 4.8×10−7 mol L−1 s−1 (B) 13.33×10−6 mol L−1 s−1 (C) 4.0×10−5 mol L−1 s−1 (D) 12.0×10−5 mol L−1 s−1
›Reveal solutionSolution
The key idea is that reaction rates for different species are linked by stoichiometric coefficients. For the reaction 5X+Y→3Z, the rate of disappearance of X is 35 times the rate of formation of Z, giving 4.0×10−5mol L−1s−1.
The core concept here is stoichiometric rate relationships. In a chemical reaction, the rate at which reactants disappear and products appear are not independent — they are tied together by the coefficients in the balanced equation. This is because for every 5 molecules of X that react, 3 molecules of Z are formed. So the rate of change of concentration for each species must be scaled by its coefficient to give the same "overall reaction rate."
Why this works:
If we define the rate of reaction as r=−51dtd[X]=−11dtd[Y]=31dtd[Z], then knowing any one of these rates lets us find the others by simple multiplication or division by the appropriate coefficient ratio.
- Write the general rate relationship For the reaction 5X+Y→3Z, the rate of reaction r is:
r=−51dtd[X]=31dtd[Z]
The negative sign indicates disappearance (decrease in concentration), while positive indicates formation.
- Identify what we know We are given the rate of formation of Z:
dtd[Z]=2.4×10−5mol L−1s−1
- Relate the rate of disappearance of X to the rate of formation of Z From the equality above:
−51dtd[X]=31dtd[Z]
Multiply both sides by −5:
dtd[X]=−35dtd[Z] …
- COMEDK 2021Set 2021-B1 markMCQQ.The equation showing the decomposition of Dinitrogen pentoxide is as follows : N2O5(g) -> N2O4(g) + 1/2 O2(g) If the initial pressure is 250 mm and after half an hour of the reaction the total pressure of the gaseous mixture is 296 mm, what is the average rate of the reaction ? (A) 4.04 * 10^-3 atm min^-1 (B) -2.02 * 10^-3 atm min^-1 (C) 2.19 * 10^-2 atm min^-1 (D) 1.09 * 10^-2 atm min^-1
›Reveal solutionSolution
The pressure rise fixes the N2O5 consumed at 92 mm; converting to atm over 30 min gives 4.04×10−3 atm min−1.
Pressure bookkeeping (N2O5→N2O4+21O2), let x = mm of N2O5 reacted:
Ptotal=(250−x)+x+2x=250+2x
250+2x=296⇒x=92 mm …
- KCET 2020Set A-11 markMCQQ.The rate constant of a reaction is given by k=PZe−Ea/RT under standard notation. In order to speed up the reaction, which of the following factors has to be decreased ? (A) T (B) Z (C) Both Z and T (D) Ea
›Reveal solutionSolution
The rate constant k increases when the activation energy Ea is decreased, because k depends exponentially on −Ea/RT; the correct answer is (D).
The Arrhenius equation k=Ae−Ea/RT (where A=PZ in the given notation) tells us exactly how temperature and activation energy control reaction speed. The exponential term e−Ea/RT is the key: it represents the fraction of molecules that have enough energy to overcome the activation barrier. To speed up a reaction, we want k to be larger — so we need that exponential term to be as large as possible.
Since the exponent is negative, making Ea smaller makes the exponent less negative, which increases e−Ea/RT. Making T larger also makes the exponent less negative (because RT is in the denominator), so increasing temperature speeds up the reaction. But the question asks which factor has to be decreased to speed up the reaction.
Let’s check each option carefully.
-
Option (A): T — Temperature appears in the denominator of the exponent. Decreasing T makes Ea/RT larger, so the exponent becomes more negative, and k gets smaller. That slows the reaction down, not speeds it up. So this is wrong.
-
Option (B): Z — Z is the collision frequency factor (part of the pre-exponential term PZ). It multiplies the exponential directly: k=(PZ)e−Ea/RT. Decreasing Z reduces the pre-factor, which reduces k. That also slows the reaction. So this is wrong too.
-
Option (C): Both Z and T — Since decreasing either one slows the reaction, decreasing both certainly won’t speed it up. This is incorrect. …
-
- KCET 2018Set A-11 markMCQQ.VERSION: 14-A 34. The temperature coefficient of a reaction is 2. When the temperature is increased from 30∘C to 90∘C, the rate of reaction is increased by (A) 150 times (B) 410 times (C) 72 times (D) 64 times
›Reveal solutionSolution
Rate ratio =(temperature coefficient)ΔT/10=260/10=26=64.
Step 1 — Meaning of the temperature coefficient.
The temperature coefficient μ of a reaction is defined as the ratio of the rate constants for a 10∘C rise:
μ=kTkT+10
For most reactions μ≈2–3 (the familiar 'rate roughly doubles for every 10∘C rise' rule). Here μ=2.
Step 2 — Count the 10∘ intervals.
ΔT=90∘C−30∘C=60∘C
n=10ΔT=1060=6
Step 3 — Compound the factor.
The effect is multiplicative, not additive — each successive 10∘ step multiplies the rate by 2 again: …
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