In a pseudo first order reaction in water, the following results were obtained:
| t/s | 0 | 30 | 60 | 90 |
|---|---|---|---|---|
| [A]/mol L−1 | 0.55 | 0.31 | 0.17 | 0.085 |
Calculate the average rate of reaction between the time interval 30 to 60 seconds.
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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.
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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 the average rate of reaction, defined as the change in concentration per unit time over a finite interval.
For the interval 30 s to 60 s:
-
Initial concentration at t=30 s: [A]30=0.31 mol L−1
Final concentration at t=60 s: [A]60=0.17 mol L−1
-
Change in concentration: Δ[A]=[A]60−[A]30=0.17−0.31=−0.14 mol L−1
-
Change in time: Δt=60−30=30 s …
The average rate of reaction is the change in concentration divided by the time interval. For the interval 30–60 s, the rate is 4.67×10−3mol L−1s−1.
The average rate of reaction tells us how fast the concentration of a reactant (or product) changes over a specific time interval. Unlike the instantaneous rate (which is the slope of the tangent at a single point), the average rate is simply the total change in concentration divided by the total time elapsed. It’s like calculating the average speed of a car on a trip — you don’t care about every bump and turn, just the total distance covered over the total time.
For a reaction A→products, the average rate over a time interval Δt=t2−t1 is:
Average rate=−ΔtΔ[A]=−t2−t1[A]t2−[A]t1
The negative sign is crucial: since [A] decreases with time, Δ[A] is negative, so the negative sign makes the rate positive. Always remember — rate is a positive quantity.
Now let’s apply this to the given data.
-
Identify the time interval and concentrations.
We need the average rate between t=30 s and t=60 s.
From the table:
[A]30=0.31mol L−1
[A]60=0.17mol L−1
-
Calculate the change in concentration.
Δ[A]=[A]60−[A]30=0.17−0.31=−0.14mol L−1
- Calculate the time interval.
Δt=60−30=30s
- Plug into the formula. Average rate=−ΔtΔ[A]=−30(−0.14)=300.14 …
Method: Average Rate of Reaction from Concentration–Time Data
The average rate of reaction is defined as the change in concentration of a reactant (or product) per unit time over a finite interval.
Steps
-
Identify the time interval
Here, the interval is from t1=30 s to t2=60 s.
-
Write the formula for average rate
For a reactant A disappearing:
Average rate=−ΔtΔ[A]
The negative sign makes the rate positive (since [A] decreases).
- Find Δ[A] and Δt
- [A] at t=30 s = 0.31 mol L−1
- [A] at t=60 s = 0.17 mol L−1
Δ[A]=0.17−0.31=−0.14 mol L−1
Δt=60−30=30 s …
Common Mistakes & How to Avoid Them
Mistake 1: Using the wrong formula for average rate
The error: Students often confuse average rate with instantaneous rate, or use the formula for rate of disappearance of reactant incorrectly.
Correct approach: Average rate of reaction over a time interval Δt is:
Average rate=−ΔtΔ[A]=−t2−t1[A]t2−[A]t1
The negative sign is crucial — it converts the negative change in reactant concentration into a positive rate.
How to avoid: Always write the formula first, then substitute values. Remember: rate is always positive.
Mistake 2: Forgetting the negative sign
The error: Students compute 60−300.17−0.31=30−0.14=−0.00467 and leave it negative.
Correct calculation:
Average rate=−60−300.17−0.31=−30−0.14=300.14=0.00467 mol L−1s−1
How to avoid: Train yourself to always include the negative sign in the formula. The final answer must be positive.
Mistake 3: Swapping the time interval order
The error: Writing 30−600.31−0.17 instead of 60−300.17−0.31.
Both give the same numerical value, but the first is mathematically incorrect and can cause sign errors in more complex problems.
How to avoid: Always use: final time−initial time[final]−[initial]
Mistake 4: Confusing average rate with rate constant
The error: Students try to use the integrated rate law for a pseudo first-order reaction:
k=t2.303log[A]t[A]0
This gives the rate constant, not the average rate.
How to avoid: Read the question carefully. "Average rate of reaction" means Δt−Δ[A], not k.
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- 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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