Q.Assertion: Order and molecularity are same.
Reason: Order is determined experimentally and molecularity is the sum of the stoichiometric coefficient of rate determining elementary step.
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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.
--- …
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] …
Concept: Average Rate of Reaction — but here the focus is on the distinction between order and molecularity.
Reasoning:
- Assertion says "Order and molecularity are same." This is false. Order can be fractional, zero, or negative; molecularity is always a positive integer (1, 2, or rarely 3) and applies only to elementary steps.
- Reason says "Order is determined experimentally and molecularity is the sum of the stoichiometric coefficients of the rate-determining elementary step." This is a correct, standard definition of both terms. …
The assertion is FALSE — order and molecularity are not, in general, the same. The reason, however, is actually a TRUE statement (it correctly defines order as experimental and molecularity as the elementary-step coefficient sum). This is an "Assertion incorrect, Reason correct" case, which is not represented by any of the four listed options exactly as worded — option (iv) as printed ("Both assertion and reason are incorrect") is not correct, because the reason itself is true. This mismatch needs review of the option text (the standard fourth choice for this assertion–reason format is normally "Assertion is incorrect but reason is correct").
Assertion — "Order and molecularity are same" — is FALSE.
- Order is an experimental quantity: the sum of the powers of the concentration terms in the observed rate law. It may be zero, a whole number, or fractional, and depends on the mechanism.
- Molecularity is a theoretical quantity defined only for an elementary step: the number of species that come together in that step. It is always a small positive integer (1, 2, or rarely 3).
Order and molecularity coincide only for a single-step (elementary) reaction; in general they differ (e.g. acid-catalysed ester hydrolysis is experimentally first order overall, even though the mechanism is multi-step). So the assertion is wrong. …
Method: Assertion–Reason Analysis
This is a concept verification method — not a calculation. The goal is to check the truth of each statement and then see if the Reason correctly explains the Assertion.
Steps
-
Check the Assertion
- Assertion: "Order and molecularity are same."
- Fact: Order and molecularity are not always the same.
- Molecularity applies only to elementary steps (and is always a small integer).
- Order is experimental and can be fractional, zero, or negative — and applies to the overall reaction.
- Result: Assertion is incorrect.
-
Check the Reason
- Reason: "Order is determined experimentally and molecularity is the sum of the stoichiometric coefficient of rate determining elementary step."
- Fact:
- Order is indeed determined experimentally. ✓ …
Here’s a breakdown of the common mistakes students make on this question, along with how to avoid each.
Mistake 1: Thinking Order and Molecularity Are Always the Same
- The error: Students assume the assertion is correct because both terms describe the number of molecules involved in a reaction. They confuse the definition of molecularity with the experimental nature of order.
- Why it’s wrong: Order can be fractional, zero, or negative — molecularity is always a positive integer (1, 2, 3). They are not the same concept.
- How to avoid: Memorise the key difference:
- Order: Sum of exponents of concentration terms in the experimentally determined rate law.
- Molecularity: Number of molecules colliding in an elementary step (only for elementary reactions).
- Example: For 2NO+O2→2NO2, the order can be 2 (experimentally), but molecularity of the rate-determining step might be 3 (if it’s a single step). They can match only for elementary reactions — not always.
Mistake 2: Misinterpreting the Reason Statement
- The error: Students think the reason is correct because “molecularity is the sum of stoichiometric coefficients of the rate-determining step” sounds familiar. They forget that molecularity is defined only for an elementary step, not for the overall reaction.
- Why it’s wrong: The reason says “sum of stoichiometric coefficients of rate determining elementary step” — this is correct for molecularity. But the assertion is false, so the reason cannot explain it.
- How to avoid: Always check the truth value of each statement separately before linking them. Write:
- Assertion: False (order ≠ molecularity in general).
- Reason: True (molecularity = sum of coefficients in the rate-determining step).
- Then decide: Since assertion is false, options (i), (ii), (iii) are all invalid. Only (iv) fits.
Mistake 3: Confusing “Correct Explanation” with “Correct Statement”
- The error: Students see both statements as individually correct and automatically pick (i) or (ii). They forget to check whether the reason actually explains the assertion.
- Why it’s wrong: Even if both were true (which they aren’t here), the reason does not explain why order and molecularity are the same — it actually highlights a difference (experimental vs theoretical).
- How to avoid: After verifying truth values, ask: “Does the reason logically lead to the assertion?” If not, even if both are true, the answer is (ii), not (i).
Mistake 4: Forgetting That Order Is Experimental, Molecularity Is Theoretical
- The error: Students treat both as theoretical concepts derived from the balanced equation.
- Why it’s wrong: Order comes from experimental data (e.g., initial rate method). Molecularity comes from mechanism (theoretical).
- How to avoid: Remember the mnemonic: Order = Observed (experiment), Molecularity = Mechanism (theory). If a question says “order is determined experimentally,” that part is always correct. …
- CBSE 2024Set B1 markQ.Write True or False: The unit of rate of reaction is mol lit^-1 sec^-1.
›Reveal solutionSolution
Rate = (change in concentration)/(time), so its unit is mol L^-1 s^-1 (or mol dm^-3 s^-1) — the statement is correct.
Rate of a chemical reaction = -(1/stoichiometric coefficient) x d[reactant]/dt = +(1/stoichiometric coefficient) x d[product]/dt. Since concentration is expressed in mo …
- CBSE 2024Set ANNUAL1 markQ.When does average rate become equal to instantaneous rate?
›Reveal solutionSolution
Average rate is a rate measured over a finite time span; as that span shrinks to zero it becomes the instantaneous rate — so the two are equal in the limit Δt→0.
The average rate of a reaction over an interval Δt=t2−t1 is:
Average rate=−ΔtΔ[R]=−t2−t1[R]2−[R]1
This is the mean rate over that whole time span and can mask how quickly the rate is actually changing within the interval.
The instantaneous rate at a specific time t is the slope of the concentration-vs-time curve at that exact point:
Instantaneous rate=−dtd[R]
Mathematically, the instantaneous rate is defined as the limit of the average rate as the time interval shrinks to zero:
Instantaneous rate=limΔt→0(−ΔtΔ[R])=−dtd[R] …
- CBSE 2023Set ANNUAL1 markMCQQ.To express the rate at a particular moment of time we determine the ________.(a) Initial rate(b) Instantaneous rate(c) Average rate(d) Standard rate
›Reveal solutionSolution
The rate 'at a particular moment' (not averaged over an interval) is called the instantaneous rate.
Average rate is calculated over a finite time interval (Delta[R]/Delta t) and changes depending on which interval is chosen. To get the rate AT one specific instant, we let the time interval shrink to zero:
…
- CBSE 2022Set E1 markMCQQ.The rate of a chemical reaction(a) increases with time(b) decreases with time(c) may increase or decrease with time(d) remains constant with time
›Reveal solutionSolution
Rate depends on reactant concentration; as reactants are consumed, concentration and hence rate fall with time.
For a typical reaction, Rate = k[reactant]^n. As the reaction proceeds the reactant concentration continuously decreases, so the rate also decreases with time (it is maximum at the start and appr …
- CBSE 2022Set ANNUAL1 markMCQQ.In the reaction 3A -> 2B, the rate of production of B is +d[B]/dt when the rate of reaction of A is(a) -(1/2) d[A]/dt(b) -(2/3) d[A]/dt(c) +2 d[A]/dt(d) -(3/2) d[A]/dt
›Reveal solutionSolution
For a reaction 3A→2B, the rate of the reaction expressed via each species must be divided by its own stoichiometric coefficient, so rates in terms of A and B are related by the ratio of those coefficients.
Setting up the rate expression: For 3A→2B, the overall rate of reaction is defined uniquely (independent of which species you track) as:
Rate=−31dtd[A]=+21dtd[B]
Solving for d[B]/dt in terms of d[A]/dt:
Given the rate of production of B is +dtd[B], equate:
21dtd[B]=−31dtd[A] …
- CBSE 2022Set ANNUAL1 markMCQQ.For a gaseous reaction, the units of rate of reaction are –(a) Latm s⁻¹(b) atm s⁻¹(c) atm mol⁻¹ s⁻¹(d) mol s⁻¹
›Reveal solutionSolution
For gaseous reactions, concentration is expressed as partial pressure, so rate has units of pressure/time.
Rate of reaction = (change in concentration)/(time). For reactions involving gases, concentration is conveniently measured as partial pressure (atm) …
- CBSE 2019Set ANNUAL1 markQ.When does the average rate of a reaction become equal to instantaneous rate?
›Reveal solutionSolution
Average rate is measured over a finite Δt; as that interval is shrunk toward zero, the average rate converges exactly to the instantaneous rate at that moment.
The average rate of a reaction over an interval is −ΔtΔ[R] (or +ΔtΔ[P]), computed using the change in concentration over a finite time interval Δt. The instantaneous rate is the rate at one particular instant, given by the derivative −dtd[R].
…
- CBSE 2018Set ANNUAL1 markQ.What is instantaneous rate of reaction?
›Reveal solutionSolution
Instantaneous rate is the rate at one exact moment, found as −d[R]/dt — the slope of the tangent drawn to the concentration-time plot at that instant (Δt → 0).
Whereas the average rate is measured over a finite time interval, the instantaneous rate is the rate of the reaction at one particular instant of time. It is obtained mathematically by making the time interval Δt infinitesimally small (Δt → 0), turning the average-rate expression into a derivative:
Instantaneous rate=limΔt→0(−ΔtΔ[R])=−dtd[R]=dtd[P] …
- CBSE 2016Set ANNUAL1 markQ.What is average rate of a reaction?
›Reveal solutionSolution
Average rate = (change in concentration) / (time interval) over a finite interval Δt.
For a reaction R → P, the average rate over the time interval t1 to t2 is
Average rate=−t2−t1[R]2−[R]1=t2−t1[P]2−[P]1=−ΔtΔ[R]=ΔtΔ[P]. …
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