Q.A first order reaction is found to have a rate constant, k=5.5×10−14 s−1. Find the half-life 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 for a first-order reaction, the half-life is independent of the initial concentration and given by a simple formula.
Step 1: Recall the half-life formula for a first-order reaction:
t1/2=kln2
Step 2: Substitute the given rate constant k=5.5×10−14 s−1:
t1/2=5.5×10−140.693
Step 3: Compute the value:
t1/2=1.26×1013 s
The half-life is 1.26×1013 s.
For a first-order reaction, the half-life is independent of initial concentration and given by t1/2=kln2. Substituting k=5.5×10−14 s−1 gives t1/2≈1.26×1013 s.
The half-life of a reaction is the time required for the concentration of a reactant to fall to half its initial value. For a first-order reaction, this quantity has a special property: it does not depend on how much reactant you start with. That’s because the rate of a first-order reaction is directly proportional to the concentration itself — so as concentration drops, the rate drops proportionally, and the time to halve is always the same.
Why does this lead to a simple formula? The integrated rate law for a first-order reaction is:
ln[A][A]0=kt
When [A]=21[A]0, the left side becomes ln2. So:
ln2=kt1/2
Rearranging gives the central result:
t1/2=kln2
Now we just plug in the given value.
- Write the formula
t1/2=kln2
- Substitute the given rate constant
t1/2=5.5×10−14 s−1ln2
- Compute ln2 — it’s approximately 0.6931.
t1/2=5.5×10−140.6931 s
- Divide the numbers
5.50.6931≈0.1260
So:
t1/2≈0.1260×1014 s=1.26×1013 s
A common mistake is to use the formula for a zero-order or second-order reaction, where half-life depends on initial concentration. Here, because it’s first-order, the half-life is constant — no initial concentration needed.
Notice the enormous half-life — over 1013 seconds. That’s roughly 400,000 years! This tells you the reaction is extremely slow, consistent with a tiny rate constant.
The half-life of the reaction is 1.26×1013 s.
Method: First-Order Half-Life Formula
For a first-order reaction, the half-life (t1/2) is independent of the initial concentration and is given by a simple formula derived from the integrated rate law.
Steps
- Recall the formula For a first-order reaction:
t1/2=kln2
- Substitute the given value Here, k=5.5×10−14 s−1
t1/2=5.5×10−14ln2
- Use ln2≈0.693
t1/2=5.5×10−140.693
- Calculate
t1/2=1.26×1013 s
Final Answer
t1/2=1.26×1013 s
Why this works
The half-life formula comes from setting [A]=21[A]0 in the first-order integrated rate law:
ln[A][A]0=kt
This gives ln2=kt1/2, so t1/2=kln2. The key insight: for first-order reactions, half-life is constant — it doesn't depend on how much reactant you start with.
Common Mistakes & How to Avoid Them
Mistake 1: Using the Wrong Formula for Half-Life
The error: Students often confuse the half-life formulas for different reaction orders. For a first order reaction, the half-life is:
t1/2=kln2
But some mistakenly use the zero-order formula (t1/2=2k[A]0) or the second-order formula (t1/2=k[A]01).
How to avoid: Memorise the key distinction — only first-order half-life is independent of initial concentration. If the question says "first order," immediately write:
t1/2=k0.693
Mistake 2: Forgetting to Use Consistent Units
The error: The rate constant is given as k=5.5×10−14 s−1. Since k is in s−1, the half-life will come out in seconds. Some students convert unnecessarily or forget to state the unit.
How to avoid: Always check the unit of k:
- If k is in s−1, t1/2 is in seconds.
- If k is in min−1, t1/2 is in minutes.
- Never mix units without conversion.
Here, the answer is simply:
t1/2=5.5×10−140.693≈1.26×1013 s
Mistake 3: Incorrect Logarithm Value or Approximation
The error: Using ln2≈0.693 is standard, but some students use log102≈0.3010 without converting. Remember:
ln2=2.303×log102≈2.303×0.3010≈0.693
How to avoid: In numerical problems, always use ln2=0.693 unless the problem explicitly uses base-10 logs. If you must use log10, multiply by 2.303.
Mistake 4: Arithmetic Errors with Powers of 10
The error: Dividing 0.693 by 5.5×10−14:
t1/2=5.5×10−140.693=5.50.693×1014
Some students mishandle the exponent — either forgetting to flip the sign or misplacing the decimal.
How to avoid: Write the division step-by-step:
- Divide the coefficients: 5.50.693≈0.126
- Handle the power: 10−141=1014
- Combine: 0.126×1014=1.26×1013
Final answer: 1.26×1013 s
Quick Revision Checklist
| Mistake | Fix |
|---|---|
| Wrong formula | Use t1/2=k0.693 only for first order |
| Unit mismatch | Match k unit → t1/2 unit |
| Wrong log value | Use ln2=0.693 |
| Exponent error | Flip sign: 10−14 in denominator → 1014 in numerator |
- 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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