Q.Which of the following expressions is correct for the rate of reaction given below?
5Br−(aq)+BrO3−(aq)+6H+(aq)→3Br2(aq)+3H2O(l)
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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 …
Why this formula?
Reaction Rate Stoichiometry: Why the Formula Holds
Let’s start with the core idea: In a chemical reaction, the rate at which reactants disappear and products appear is not arbitrary — it is tied directly to the stoichiometric coefficients in the balanced equation.
The Key Formula
For a general reaction:
aA+bB→cC+dD
The rate of reaction (R) is defined as:
R=−a1dtd[A]=−b1dtd[B]=c1dtd[C]=d1dtd[D]
Where:
- [A],[B],[C],[D] are concentrations (in mol/L)
- t is time
- a,b,c,d are stoichiometric coefficients
Why This Formula Holds: The Reasoning
1. The Physical Meaning of Stoichiometric Coefficients
The coefficients tell us the mole ratio in which substances react or are produced. For example:
2H2+O2→2H2O
- 2 moles of H2 react with 1 mole of O2 to produce 2 moles of H2O.
- This means: for every 2 molecules of H2 that disappear, only 1 molecule of O2 disappears, and 2 molecules of H2O appear.
Key insight: The number of moles changing per unit time is different for each substance, but the reaction event is the same.
2. The Problem with Raw Rates
If we simply wrote:
Rate=−dtd[H2]
This would be twice the rate of disappearance of O2 (since H2 disappears twice as fast). That’s inconsistent — the same reaction shouldn’t have two different numerical rates.
We need a single, unique rate that describes the reaction itself, not just one substance.
3. The Solution: Normalize by Stoichiometric Coefficients
To get a reaction rate that is the same regardless of which substance we track, we divide each substance’s rate of change by its stoichiometric coefficient.
Why division works:
- If A disappears at rate −dtd[A], and a moles of A are consumed per reaction event, then the number of reaction events per unit time is:
Reaction events per second=a−dtd[A]
- Similarly, for product C appearing at rate +dtd[C], with c moles produced per event:
Reaction events per second=c+dtd[C]
Since the same reaction is happening, these must be equal. Hence:
−a1dtd[A]=c1dtd[C]
4. The Sign Convention
- Reactants decrease over time → dtd[reactant]<0 → we add a negative sign to make the rate positive.
- Products increase over time → dtd[product]>0 → we use a positive sign. …
Concept: Reaction Rate Stoichiometry – For a balanced reaction, the rate of disappearance of any reactant is related to the rate of disappearance of another by their stoichiometric coefficients.
Step 1: Write the general rate expression. For the reaction
5Br−+BrO3−+6H+→3Br2+3H2O,
the rate is:
−51ΔtΔ[Br−]=−61ΔtΔ[H+]
Step 2: Solve for ΔtΔ[Br−] in terms of ΔtΔ[H+]. Multiply both sides by −5:
ΔtΔ[Br−]=65ΔtΔ[H+] …
The rate of a reaction is defined per stoichiometric coefficient, so the rate of disappearance of Br− divided by 5 equals the rate of disappearance of H+ divided by 6. This gives ΔtΔ[Br−]=65ΔtΔ[H+], which is option (iii).
The key idea here is that the rate of a reaction is a single, unified quantity — it doesn't depend on which reactant or product you measure, as long as you account for the stoichiometric coefficients. For the reaction
5Br−+BrO3−+6H+→3Br2+3H2O,
the rate can be written as:
Rate=−51ΔtΔ[Br−]=−61ΔtΔ[H+]
The negative signs indicate that concentrations of reactants decrease over time. Since both expressions equal the same rate, we can set them equal to each other (ignoring the negative signs, as they cancel):
51ΔtΔ[Br−]=61ΔtΔ[H+]
Now multiply both sides by 5:
ΔtΔ[Br−]=65ΔtΔ[H+]
That matches option (iii). …
Method: Stoichiometric Rate Relation
This method uses the fundamental rule that for any reaction:
aA+bB→cC+dD
the rate can be written in terms of any reactant or product as:
−a1ΔtΔ[A]=−b1ΔtΔ[B]=+c1ΔtΔ[C]=+d1ΔtΔ[D]
The negative sign is used for reactants (they are disappearing), and the positive sign for products (they are appearing).
Steps for this problem
Step 1: Write the given reaction:
5Br−+BrO3−+6H+→3Br2+3H2O
Step 2: Apply the stoichiometric rate relation between Br− and H+ (both are reactants, so both get negative signs):
−51ΔtΔ[Br−]=−61ΔtΔ[H+] …
Common Mistakes & How to Avoid Them
Mistake 1: Confusing the sign convention
The error: Students often forget that reactants have a negative sign in the rate expression. They write:
ΔtΔ[Br−]=+65ΔtΔ[H+]
But since both Br− and H+ are reactants, their concentrations decrease with time — both Δ[Br−] and Δ[H+] are negative. The correct relationship must account for this.
How to avoid: Always write the definition of rate first:
−51ΔtΔ[Br−]=−61ΔtΔ[H+]
Cancel the negative signs on both sides, then solve:
ΔtΔ[Br−]=65ΔtΔ[H+]
Answer: Option (iii) is correct.
Mistake 2: Inverting the stoichiometric ratio
The error: Students often write the ratio backwards — putting the coefficient of the substance they are solving for in the denominator instead of the numerator.
For example, they might write:
ΔtΔ[Br−]=56ΔtΔ[H+]
This is wrong because the rate definition gives:
−51ΔtΔ[Br−]=−61ΔtΔ[H+]
Multiplying both sides by 5 gives:
ΔtΔ[Br−]=65ΔtΔ[H+]
How to avoid: Use the formula method:
ΔtΔ[A]=coefficient of Bcoefficient of A×ΔtΔ[B]
Here, coefficient of Br− is 5, coefficient of H+ is 6, so:
ΔtΔ[Br−]=65ΔtΔ[H+]
Mistake 3: Forgetting to use the rate definition as the starting point …
- KEAM 2026Set eng-2026-04184 marksMCQQ.The first order reaction N2O5→2NO2+21O2, is carried out in a closed container and there were no products initially. When it is heated at constant volume the final pressure of the system on 75% completion of the reaction is (A) 2.5 times initial pressure (B) 3.5 times initial pressure (C) 3 times initial pressure (D) 2 times initial pressure (E) 4 times initial pressure
›Reveal solutionSolution
Track partial pressures at 75% decomposition of N2O5; total ≈2.1 times the initial pressure.
Reaction: N2O5→2NO2+21O2, initial pressure P (only N2O5).
At 75% completion, 0.75P of N2O5 decomposes:
- N2O5 left =0.25P
- NO2 formed =2×0.75P=1.5P
- O2 formed =0.5×0.75P=0.375P …
- KEAM 2025Set pha-2025-0429F4 marksMCQQ.In a reaction, 3A → Products, the concentration of 'A' decreases from 0.6 mol L−1 to 0.3 mol L−1 in 20 minutes. What is the rate of the reaction during this interval? (A) 0.05 mol L−1min−1 (B) 0.005 mol L−1min−1 (C) 0.03 mol L−1min−1 (D) 0.6 mol L−1min−1 (E) 0.003 mol L−1min−1
›Reveal solutionSolution
For 3A→ products, rate =−31ΔtΔ[A]. With Δ[A]=−0.3 mol L⁻¹ over 20 min, rate =0.005 mol L⁻¹ min⁻¹.
Reasoning
The stoichiometric coefficient of A is 3, so the reaction rate is
Rate=−31ΔtΔ[A] …
- KEAM 2021Set eng-2021-P1-A14 marksMCQQ.For the reaction 2P+Q⇌P2Q, the rate of formation of P2Q is 0.24 mol dm−3s−1. Then the rates of disappearance of P and Q respectively are (A) −0.48 mol dm−3s−1 and −0.48 mol dm−3s−1 (B) −0.24 mol dm−3s−1 and −0.48 mol dm−3s−1 (C) −0.48 mol dm−3s−1 and −0.24 mol dm−3s−1 (D) −0.12 mol dm−3s−1 and −0.24 mol dm−3s−1 (E) −0.24 mol dm−3s−1 and −0.12 mol dm−3s−1
›Reveal solutionSolution
P disappears at −0.48 and Q at −0.24 mol dm−3s−1.
Concept and Intuition
Rates for reactants and products are linked by stoichiometric coefficients: rate =−21dtd[P]=−dtd[Q]=+dtd[P2Q].
Step-by-Step Solution
- Given dtd[P2Q]=0.24 mol dm−3s−1.
- −dtd[P]=2×0.24=0.48 (P has coefficient 2).
- −dtd[Q]=0.24 (Q has coefficient 1). …
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