Q.Following reaction takes place in one step : 2A+B⟶2C How will the rate of above reaction change if the volume of the reaction vessel is decreased to one third of its original volume ? Will there be any change in the order of reaction with the reduced volume ?
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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. …
The key idea is Reaction Rate Stoichiometry and how concentration changes with volume.
-
For a one-step (elementary) reaction, the rate law is directly from the stoichiometric coefficients:
Rate=k[A]2[B].
-
When volume is reduced to 31, concentration of each gas increases by a factor of 3 (since [X]=Vn). So:
[A]new=3[A], [B]new=3[B].
-
New rate:
Ratenew=k(3[A])2(3[B])=27⋅k[A]2[B]=27×Rateoriginal. …
For an elementary (one-step) reaction, the rate law is directly derived from the stoichiometric coefficients. Halving the volume triples all concentrations, so the rate increases by a factor of 33=27. The order of the reaction remains unchanged because it is an intrinsic property of the reaction mechanism, not the volume.
Why the stoichiometry gives the rate law
When a reaction occurs in a single step (elementary reaction), the rate law is simply the product of the reactant concentrations raised to their stoichiometric coefficients. This is because the reaction mechanism is exactly the balanced equation — there are no intermediate steps or rate-determining approximations.
For the reaction
2A+B⟶2C
the rate law is therefore:
Rate=k[A]2[B]1
The overall order of the reaction is the sum of the exponents: 2+1=3 (third order).
The order of an elementary reaction is always equal to the molecularity (the number of molecules colliding). Here, three molecules must collide simultaneously — two of A and one of B — so the reaction is termolecular and third order.
How volume change affects concentration and rate
- Relating volume to concentration Concentration is moles per unit volume: [X]=VnX. If the volume is decreased to one-third, the new volume is V′=3V. Since the number of moles of each reactant remains the same (no reaction has occurred yet), the new concentrations become:
[A]′=V/3nA=3⋅VnA=3[A]
[B]′=V/3nB=3[B]
So each concentration triples.
- Substitute into the rate law Original rate: R=k[A]2[B] New rate after volume reduction:
R′=k(3[A])2(3[B])=k⋅9[A]2⋅3[B]=27k[A]2[B]=27R
The rate increases by a factor of 27. …
- CBSE 2026Set 56/3/11 markMCQQ.For a reaction 3A→2B, the rate of reaction +dtd[B] is equal to : (A) −23dtd[A] (B) −32dtd[A] (C) −31dtd[A] (D) +2dtd[A]
›Reveal solutionSolution
The rate of change of concentration of a species is related to the overall reaction rate by its stoichiometric coefficient; for 3A→2B, the rate of formation of B is −32dtd[A].
In chemical kinetics, the rate of a reaction can be expressed in terms of the rate of disappearance of reactants or the rate of formation of products. However, these individual rates are not always equal to each other because of the stoichiometry of the reaction. For example, if 3 moles of A disappear for every 2 moles of B formed, then A is disappearing faster than B is forming (in terms of moles).
To define a single, unambiguous "rate of reaction" for the entire process, we normalize the rate of change of concentration of each species by its stoichiometric coefficient. This ensures that the overall reaction rate is independent of which reactant or product we choose to monitor.
For a general reaction aA+bB→cC+dD, the rate of reaction is given by:
Rate=−a1dtd[A]=−b1dtd[B]=+c1dtd[C]=+d1dtd[D]
The negative sign for reactants indicates their concentration decreases over time, while the positive sign for products indicates their concentration increases.
Let's apply this concept to the given reaction.
- Write the general rate expression for the given reaction. The reaction is 3A→2B. Using the general formula, the rate of reaction can be expressed in terms of the disappearance of A and the formation of B:
Rate=−31dtd[A]=+21dtd[B]
Here, $\frac{d[A]}{dt}$ represents the instantaneous rate of change of concentration of A, and $\frac{d[B]}{dt}$ represents the instantaneous rate of change of concentration of B. The negative sign for A indicates it is a reactant and its concentration is decreasing. The positive sign for B indicates it is a product and its concentration is increasing.2. Equate the relevant parts of the rate expression and solve for the desired term. …
- CBSE 2026Set 56/2/11 markMCQQ.The order for the given reaction is : A+2B→ Products Rate =k[A]1/2[B]1 (A) 1.5 (B) 1 (C) 0.5 (D) 2
›Reveal solutionSolution
The order of a reaction is the sum of all exponents in the rate law. Here, 21+1=23=1.5, so the answer is (A).
Understanding Reaction Order
The order of a reaction tells us how the rate depends on reactant concentrations. It's a purely experimental quantity—you cannot deduce it from the stoichiometric equation alone. The stoichiometric coefficients (1 for A, 2 for B) are irrelevant here; only the exponents in the experimentally determined rate law matter.
When we write a rate law like Rate=k[A]m[B]n, the exponents m and n describe how sensitive the rate is to changes in each reactant's concentration. The overall order is simply the sum of these individual orders.
Finding the Overall Order
The rate law given is:
Rate=k[A]1/2[B]1
Let's identify each component:
-
Order with respect to A: The exponent on [A] is 21. This means the reaction is half-order in A—if you quadruple the concentration of A (keeping B constant), the rate only doubles.
-
Order with respect to B: The exponent on [B] is 1. This means the reaction is first-order in B—doubling B doubles the rate (keeping A constant).
-
Overall order: Add the individual orders:
Overall order=21+1=23=1.5 …
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- CBSE 2026Set A1 markMCQQ.For a reaction, aA + bB -> products, -d[A]/dt is equal to(a) -d[B]/dt(b) (-b/d) d[B]/dt(c) (-a/b) d[B]/dt(d) (-b/a) d[B]/dt
›Reveal solutionSolution
Rate = -(1/a) d[A]/dt = -(1/b) d[B]/dt, so -d[A]/dt = (a/b)(-d[B]/dt) = (-a/b) d[B]/dt, which is option (c).
For aA + bB -> products, the rate of reaction is defined so that
Rate = -(1/a) d[A]/dt = -(1/b) d[B]/dt.
Equating the two: (1/a)(-d[A]/dt) = (1/b)(-d[B]/dt), hence
-d[A]/dt = (a/b)(-d[B]/dt) = (-a/b) d[B]/dt. …
- CBSE 2025Set ANNUAL1 markQ.In the reaction BrO3−(aq)+5Br−(aq)+6H+→3Br2(l)+3H2O(l) how is rate of appearance of bromine related to the rate of disappearance of bromide ion ?
›Reveal solutionSolution
Dividing each species' rate of change by its own stoichiometric coefficient gives a common "rate of reaction" expression, which links the rates of Br₂ formation and Br⁻ consumption via a 3:5 ratio.
For the balanced reaction:
BrO3−(aq)+5Br−(aq)+6H+→3Br2(l)+3H2O(l)
The rate of reaction, expressed consistently for every species, divides each species' rate of change by its own stoichiometric coefficient:
Rate=31dtd[Br2]=−51dtd[Br−]
Rearranging to relate the two rates directly:
dtd[Br2]=−53dtd[Br−]
…
- CBSE 2024Set 56/1/11 markMCQQ.For the reaction X+2Y→P, the differential form equation of the rate law is: (A) dt2d[P]=−dtd[Y] (B) −dtd[P]=−dtd[X] (C) +dtd[X]=−dtd[P] (D) −2dtd[Y]=+dtd[P]
›Reveal solutionSolution
The stoichiometric coefficients relate the rates of change of all species in a reaction; for X+2Y→P, the rate of consumption of Y is twice the rate of formation of P, giving −2dtd[Y]=+dtd[P].
Understanding Reaction Rate Stoichiometry
When a chemical reaction proceeds, the concentrations of reactants decrease while products increase. The rate at which each species changes is directly tied to the stoichiometric coefficients in the balanced equation. The key insight is that these rates must be proportional to maintain the stoichiometry throughout the reaction.
For a general reaction aA+bB→cC+dD, the relationship between the rates of change is:
−a1dtd[A]=−b1dtd[B]=+c1dtd[C]=+d1dtd[D]
The negative signs appear for reactants (concentrations decreasing), positive for products (concentrations increasing). Dividing by the stoichiometric coefficient normalizes the rate to a common "reaction rate."
Step-by-Step Analysis
-
Identify the stoichiometry
For X+2Y→P, we have:
- 1 mole of X consumed
- 2 moles of Y consumed
- 1 mole of P formed
-
Write the general rate relationship
Applying the stoichiometric rate law:
−dtd[X]=−21dtd[Y]=+dtd[P]
Each term equals the overall reaction rate. Notice Y has coefficient 2, so its rate of change is divided by 2.
-
Extract pairwise relationships
From the equality above, we can derive several equivalent statements:
- Between Y and P: −21dtd[Y]=+dtd[P]
Multiplying both sides by −2:
−2dtd[Y]=+dtd[P]
- Check each option …
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- CBSE 2024Set 56/2/11 markMCQQ.For the elementary reaction P→Q, the rate of disappearance of 'P' increases by a factor of 8 on doubling the concentration of 'P'. The order of the reaction with respect to 'P' is : (A) 3 (B) 4 (C) 2 (D) 1
›Reveal solutionSolution
When the concentration of P doubles and the rate increases by a factor of 8, the reaction is third order with respect to P. The answer is (A) 3.
Understanding Rate Laws and Reaction Order
The rate of a reaction tells us how fast a reactant disappears or a product forms. For an elementary reaction, the rate law can be written directly from the stoichiometry. For P→Q, the rate of disappearance of P is:
Rate=k[P]n
where k is the rate constant and n is the order of the reaction with respect to P. The order tells us how sensitive the rate is to changes in concentration.
The key insight here is that if we know how the rate changes when concentration changes, we can deduce the order. Specifically, if concentration is multiplied by some factor, the rate is multiplied by that factor raised to the power of the order.
Finding the Order Step by Step
- Write the rate law at the initial concentration Let the initial concentration of P be [P]0. The initial rate is:
Rate1=k[P]0n
- Write the rate law at the doubled concentration When we double the concentration, [P]=2[P]0. The new rate is:
Rate2=k(2[P]0)n=k⋅2n⋅[P]0n
- Set up the ratio of rates We're told that the rate increases by a factor of 8, meaning Rate2=8×Rate1. Taking the ratio:
Rate1Rate2=k[P]0nk⋅2n⋅[P]0n=2n
- Solve for the order …
- CBSE 2024Set ANNUAL1 markMCQQ.For the reaction : 4NH3(g) + 5O2(g) -> 4NO(g) + 6H2O(g), the rate of formation of NO is 3.6 x 10-3 mol L-1 S-1. The rate of disapperance of ammonia would be -(a) 5.4 x 10-3 mol L-1 S-1(b) 2.4 x 10-3 mol L-1 S-1(c) 3.6 x 10-3 mol L-1 S-1(d) 4.6 x 10-3 mol L-1 S-1
›Reveal solutionSolution
Because NH3 and NO both have coefficient 4 in the balanced equation, their rates of change are numerically equal.
For the reaction 4NH3(g)+5O2(g)→4NO(g)+6H2O(g), the rate of reaction is written in terms of each species divided by its stoichiometric coefficient:
Rate=−41dtd[NH3]=−51dtd[O2]=41dtd[NO]=61dtd[H2O]
Since NH3 (a reactant) and NO (a product) both carry the coefficient 4: …
- CBSE 2023Set 56/2/11 markMCQQ.For the reaction 3A→2B, rate of reaction +dtd[B] is equal to (A) −23dtd[A] (B) −32dtd[A] (C) −31dtd[A] (D) +2dtd[A]
›Reveal solutionSolution
The rate of formation of B is linked to the rate of consumption of A through their stoichiometric coefficients: dtd[B]=−32dtd[A]. The answer is (B).
Understanding Reaction Rate Stoichiometry
When a chemical reaction proceeds, different species appear or disappear at rates determined by the balanced equation. The stoichiometric coefficients tell us the ratio in which molecules react and form, but the actual rates of change of concentration must account for these ratios.
For the reaction 3A→2B, three molecules of A disappear for every two molecules of B that form. This means A is consumed 23 times faster than B is produced. The key insight: to define a single "rate of reaction" that's the same no matter which species we measure, we divide each species' rate by its stoichiometric coefficient.
The general relationship is:
Rate=−31dtd[A]=+21dtd[B]
The negative sign appears for reactants (concentration decreasing) and positive for products (concentration increasing).
Step-by-Step Solution
- Write the stoichiometric relationship From 3A→2B, the stoichiometric coefficients are 3 for A and 2 for B. The rate of reaction is defined as:
Rate=−31dtd[A]=+21dtd[B]
- Isolate dtd[B] We want to express dtd[B] in terms of dtd[A]. From the equality above:
21dtd[B]=−31dtd[A]
- Solve for dtd[B] Multiply both sides by 2: …
- CBSE 2023Set F1 markMCQQ.The rate of chemical reaction, 2A+B→C can be represented by which of the following?(a) -1/2 d[A]/dt(b) -d[B]/dt(c) +d[C]/dt(d) All of these
›Reveal solutionSolution
Rate is defined so that each species term is divided by its stoichiometric coefficient; all three given forms are equal.
For the reaction 2A + B → C, the unique rate of reaction is written by dividing each concentration change by the corresponding stoichiometric coefficient (with a minus sign for reactants):
Rate = -(1/2) d[A]/dt = -d[B]/dt = +d[C]/dt
- A has coefficient 2, so its term is -(1/2) d[A]/dt. …
- CBSE 2020Set ANNUAL1 markQ.Clculate the rate of the reaction, A + 2B -> 2C + D.
›Reveal solutionSolution
For a general reaction, the rate is defined as the rate of change of concentration of any species divided by its stoichiometric coefficient, with reactants taken as negative (since they are consumed) and products as positive (since they are formed).
For the reaction A + 2B -> 2C + D, the stoichiometric coefficients are 1 (A), 2 (B), 2 (C), and 1 (D). By definition, the rate of reaction is the same value whichever species you track, once each rate-of-change term is divided by its own coefficient:
Rate = -d[A]/dt = -(1/2) d[B]/dt = (1/2) d[C]/dt = d[D]/dt
…
- CBSE 2018Set ANNUAL1 markMCQQ.For the reaction, 2A+B⟶3C+D, which of the following does NOT express the reaction rate ?(a) 2dt−d[A](b) dt−d[B](c) 3dt−d[C](d) 3dt−d[D]
›Reveal solutionSolution
The correct rate expressions divide by each species' own stoichiometric coefficient — D's coefficient is 1, so dividing by 3 is wrong.
For 2A+B→3C+D, the rate of reaction is expressed as:
Rate=−21dtd[A]=−dtd[B]=31dtd[C]=dtd[D]
each concentration-change term divided by its own stoichiometric coefficient (2 for A, 1 for B, 3 for C, 1 for D), with a negative sign for reactants being consumed and a positive sign for products being formed.
…
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