Q.For a reaction, A+B→ Product; the rate law is given by, r=k[A]1/2[B]2. What is the order of the reaction?
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.
Common Pitfall to Avoid
Do not write dtd[reactant] as a positive number and then forget the minus sign. The rate of change of a reactant is negative (concentration falls). The minus sign in the definition flips it to a positive r. If you skip the sign, you will get the wrong magnitude for other species.
Why This Matters
In exams (JEE, NEET, etc.), you will often be given the rate for one species and asked to find the rate for another. The stoichiometric relation is the only tool you need — no extra formulas. It also appears in more advanced topics like the rate law (where the exponents are not the coefficients) — but that is a separate concept. Reaction rate stoichiometry is purely about the definition of the reaction rate itself.
Final takeaway: The coefficients in the balanced equation are the conversion factors between the rates of different species. Always normalise by dividing by the coefficient to get the universal reaction rate r.
Average rate of reaction is one of the first ideas introduced in the NCERT/CBSE Class 12 Chemistry Chemical Kinetics chapter, and ‘average rate of reaction formula’ or ‘average vs instantaneous rate’ are common important-question topics in board exams and JEE Main chemistry. A solid grasp of this basic definition is also assumed in nearly every subsequent kinetics numerical asked in NEET and state CETs.
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]
- νX is negative for reactants → the minus sign is already built in.
- νX is positive for products.
6. Why this is the average rate (not instantaneous)
- Average rate uses a finite Δt — it’s the slope of the chord between two points.
- Instantaneous rate uses Δt→0 — it’s the slope of the tangent at a single point.
The average rate formula is just the discrete version of the derivative:
Instantaneous rate=νX1dtd[X]
Summary — the "why" in one sentence
The average rate formula holds because it measures change in concentration per unit time, uses a minus sign to keep rates positive for reactants, and divides by stoichiometric coefficients to give a single, comparable value for the whole reaction.
Always remember:
- Δ[reactant] is negative → minus sign makes it positive.
- Δ[product] is positive → no minus sign.
- Divide by coefficient → normalise to "per mole of reaction".
The key idea is that the order of a reaction is the sum of the exponents of the concentration terms in the experimentally determined rate law.
Reasoning:
- The rate law is r=k[A]1/2[B]2.
- The exponent of [A] is 21, and the exponent of [B] is 2.
- The overall order is the sum of these exponents: 21+2=2.5.
The order of the reaction is 2.5.
The order of a reaction is the sum of the exponents in its rate law. For r=k[A]1/2[B]2, the order is 1/2+2=2.5, so the reaction is of 2.5 order.
The order of a reaction tells you how the rate depends on the concentration of each reactant. It’s not something you guess from the balanced equation — it comes directly from the experimentally determined rate law. Here, the rate law is given: r=k[A]1/2[B]2.
The exponent on [A] is 1/2, meaning if you double [A], the rate increases by a factor of 21/2≈1.41. The exponent on [B] is 2, so doubling [B] quadruples the rate. The overall order is simply the sum of these individual exponents.
-
Identify the exponents in the rate law:
For [A], exponent = 21.
For [B], exponent = 2.
-
Add them:
21+2=21+24=25=2.5.
-
That’s the overall order of the reaction.
A common mistake is to think the order comes from the stoichiometric coefficients (1 for A, 1 for B) — that would give order 2, which is wrong. The rate law is experimental; coefficients are irrelevant unless the reaction is elementary (and even then, you’d check).
Fractional orders like 1/2 are common in complex reactions (e.g., involving dissociation or adsorption). Don’t be thrown off — just sum the exponents as given.
The order of the reaction is 2.5.
Method: Sum of Exponents (Order from Rate Law)
The order of a reaction is the sum of the powers (exponents) of the concentration terms in the experimentally determined rate law.
Steps
-
Write the given rate law
r=k[A]1/2[B]2
-
Identify the exponents
- Exponent of [A] = 21
- Exponent of [B] = 2
-
Add the exponents
Order=21+2=21+24=25
-
State the result
The overall order of the reaction is 25 (or 2.5).
Key Exam Tip
- The order is not the same as the stoichiometric coefficients (here, both are 1 from the balanced equation, but the order is 2.5).
- Order is experimentally determined from the rate law, not from the balanced chemical equation.
Here are the common mistakes students make when determining the order of a reaction from a rate law like r=k[A]1/2[B]2, and how to avoid each.
Mistake 1: Forgetting to add the exponents
What students do wrong:
They see [A]1/2 and [B]2, and answer “order = 2” (only looking at [B]) or “order = 1/2” (only looking at [A]).
Why it’s wrong:
The overall order is the sum of all exponents in the rate law.
How to avoid:
Always write the sum explicitly:
Order=21+2=25 or 2.5
Key rule: Overall order = sum of powers of all concentration terms in the rate law.
Mistake 2: Confusing stoichiometric coefficients with exponents
What students do wrong:
They see A+B→Product and think the order is 1+1=2 (from the balanced equation).
Why it’s wrong:
The rate law is determined experimentally, not from the balanced chemical equation. The exponents in the rate law are not the stoichiometric coefficients.
How to avoid:
- Ignore the balanced equation when finding order from a given rate law.
- Only look at the exponents in r=k[A]1/2[B]2.
Key rule: Order comes from the rate law, not the reaction equation.
Mistake 3: Misreading fractional exponents
What students do wrong:
They treat [A]1/2 as [A]1 or [A]2, or think 1/2 means “half-order” is not a valid order.
Why it’s wrong:
Fractional orders (like 1/2, 3/2) are perfectly valid in chemical kinetics.
How to avoid:
- Treat 1/2 as a number: 0.5.
- Add it normally: 0.5+2=2.5.
Key rule: Orders can be integers, fractions, or even zero — just add the numbers as given.
Mistake 4: Forgetting to include the constant k in the order
What students do wrong:
They think k has an exponent that contributes to the order.
Why it’s wrong:
k is the rate constant — it is a proportionality factor, not a concentration term. Its units change with order, but its exponent does not add to the order.
How to avoid:
- Only look at the exponents on [A], [B], etc.
- k is just a multiplier; ignore it when summing exponents.
Key rule: Order depends only on concentration exponents, not on k.
Quick Summary Checklist
| Mistake | How to Avoid |
|---|---|
| Only one exponent | Sum all exponents |
| Using stoichiometry | Use only the rate law |
| Misreading fractions | Treat 1/2 as 0.5 |
| Including k | Ignore k entirely |
Final answer for this question:
Order=21+2=25=2.5
- GSEB Higher Secondary Certificate (HSC) Examination 2026Set ANNUAL1 markMCQQ.In a reaction 2HI -> H2 + I2, the concentration of HI decreases from 0.5 mol L^-1 to 0.4 mol L^-1 in 10 minutes. What is the rate of reaction during this interval?(a) 5 x 10^-3 M min^-1(b) 2.5 x 10^-3 M min^-1(c) 5 x 10^-2 M min^-1(d) 2.5 x 10^-2 M min^-1
›Reveal solutionSolution
For 2HI → H2 + I2, the rate of reaction is defined using the stoichiometric coefficient of HI: Rate = −(1/2)(Δ[HI]/Δt).
Given: [HI] falls from 0.5 mol L⁻¹ to 0.4 mol L⁻¹ over 10 minutes.
Δ[HI] = 0.4 − 0.5 = −0.1 mol L⁻¹, over Δt = 10 min
Since 2 mol of HI are consumed for every 1 unit of reaction progress, the rate of reaction is:
Rate = −(1/2) × (Δ[HI]/Δt) = −(1/2) × (−0.1/10) = −(1/2) × (−0.01) = 0.005 mol L⁻¹ min⁻¹ = 5 × 10⁻³ M min⁻¹
✓Final answer(a) 5 x 10^-3 M min^-1.
- GUJCET 2023Set 091 markMCQQ.Which will be the unit of rate constant for the reaction having Rate =K[A]1/2[B]3/2? (A) Second−1 (B) Mol/lit.Sec−1 (C) Mol−1.lit.Sec−1 (D) (Mol/lit)2.Sec−1
›Reveal solutionSolution
Unit of k for order n is (mol L−1)1−ns−1.
Concept: Overall order =21+23=2. For a second-order reaction,
[k]=(mol L−1)1−2s−1=mol−1Ls−1.
✓Final answer(C) Mol−1.lit.Sec−1
ANSWER: (C)
- GUJCET 2021Set 151 markMCQQ.For a reaction, K=4.5×10−4 L mol−1 s−1. What is order of reaction? (A) Zero (B) Second (C) First (D) Third
›Reveal solutionSolution
Units L mol−1s−1 = M−1s−1 ⇒ second order.
Concept: The unit of a rate constant is mol1−nLn−1s−1 for order n. Solving Lmol−1s−1:
1−n=−1⇒n=2
✓Final answer(B) Second
ANSWER: (B)
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