Q.Calculate the half-life of a first order reaction from their rate constants given below:
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First Order Kinetics
Imagine you have a bucket of water with a small hole at the bottom. The water drains out. At the start, the bucket is full, so the pressure at the hole is high — water gushes out fast. As the water level drops, the pressure decreases, and the water trickles out more slowly. The rate at which water leaves is directly proportional to how much water is still in the bucket.
That's the core intuition behind first order kinetics: the rate of a process depends linearly on how much of the substance is left.
The Precise Statement
In chemistry, first order kinetics describes a reaction where the rate of the reaction is directly proportional to the concentration of one reactant.
If we have a reaction: A→products, then:
Rate=−dtd[A]=k[A]
Here:
- [A] is the concentration of reactant A at any time t
- k is the rate constant (units: time−1, e.g., s−1)
- The negative sign indicates that [A] decreases over time
The key point: double the concentration, double the rate. Halve the concentration, halve the rate.
The Integrated Form — What Actually Happens Over Time
The differential equation above tells us the instantaneous rate. But what we usually want is: how does concentration change with time?
Integrating gives:
ln[A]t=ln[A]0−kt
or equivalently:
[A]t=[A]0e−kt
Where [A]0 is the initial concentration and [A]t is the concentration at time t.
This exponential decay is the hallmark of first order kinetics. The concentration drops rapidly at first, then more slowly, approaching zero asymptotically.
The Half-Life — A Beautiful Constant
For first order kinetics, the half-life (t1/2) — the time taken for half the reactant to be consumed — is independent of the starting concentration.
t1/2=kln2≈k0.693
This is a powerful result. Whether you start with 100 g or 1 g, it always takes the same time to go from that amount to half of it. This is unique to first order kinetics — no other order has this property.
For a first order process, after n half-lives, the fraction remaining is (21)n. After 1 half-life: 50% remains. After 2: 25%. After 3: 12.5%. And so on.
How to Identify First Order Kinetics Experimentally
If you plot ln[A] versus time and get a straight line with slope −k, the reaction is first order. This is the gold standard test.
Alternatively, if the half-life remains constant as you change the initial concentration, that's a strong indicator.
Real-World Examples
- Radioactive decay: Every radioactive isotope decays by first order kinetics. Carbon-14 dating works because t1/2=5730 years, regardless of how much carbon-14 is present. …
Why this formula?
First Order Kinetics: Why the Formula Holds
Let's build this from the core idea — not just memorise the equation.
The Fundamental Assumption
In a first order reaction, the rate of reaction depends linearly on the concentration of only one reactant.
If we have:
A→products
The rate law is:
Rate=−dtd[A]=k[A]
Here:
- −dtd[A] = rate of disappearance of A (negative because [A] decreases)
- k = rate constant (units: time−1, e.g., s−1)
- [A] = concentration of A at any time
Why linear? Because the probability of a single molecule reacting in a given time is constant — it doesn't depend on other molecules. This is the molecular logic behind first order.
Deriving the Integrated Rate Law
We start from the differential form:
−dtd[A]=k[A]
Step 1: Separate variables
Bring all [A] terms to one side, dt to the other:
[A]d[A]=−kdt
Step 2: Integrate both sides
Integrate from initial time t=0 (concentration [A]0) to any time t (concentration [A]t):
∫[A]0[A]t[A]d[A]=−k∫0tdt
The left side integrates to ln[A]:
ln[A]t−ln[A]0=−kt
Step 3: Rearrange
ln[A]0[A]t=−kt
Or equivalently:
ln[A]t=ln[A]0−kt
This is the integrated rate law for first order kinetics.
Why This Form Makes Sense
- Exponential decay: Taking antilog:
[A]t=[A]0e−kt
The concentration decays exponentially — a hallmark of first order processes.
- Constant half-life: The time for [A]t to become half of [A]0 is:
2[A]0=[A]0e−kt1/2
21=e−kt1/2
ln(21)=−kt1/2
t1/2=kln2
Key insight: t1/2 is independent of initial concentration — unique to first order. This is why radioactive decay (a first order process) has a fixed half-life regardless of how much you start with.
Graphical Interpretation (Exam-Ready) …
Concept: First Order Kinetics
For a first-order reaction, the half-life (t1/2) is independent of initial concentration and given by:
t1/2=kln2=k0.693
Step 1 – Apply the formula
Substitute each rate constant k into t1/2=0.693/k.
Step 2 – Compute each case
- k=200 s−1:
t1/2=2000.693=0.003465 s
- k=2 min−1: t1/2=20.693=0.3465 min …
For a first-order reaction, half-life is independent of concentration and given by t1/2=kln2. Using the given rate constants, the half-lives are (i) 3.47×10−3 s, (ii) 0.347 min, and (iii) 0.173 years.
Why half-life is constant for first-order reactions
In a first-order reaction, the rate depends linearly on the concentration of one reactant:
Rate=k[A].
The integrated rate law is [A]=[A]0e−kt. Half-life is the time when [A]=21[A]0. Substituting gives 21[A]0=[A]0e−kt1/2, so e−kt1/2=21. Taking natural logs: −kt1/2=ln21=−ln2. Hence:
t1/2=kln2
This is the central result. Notice that ln2≈0.693. The half-life depends only on k, not on the starting amount — that’s the hallmark of first-order kinetics.
Step-by-step calculation
1. For k=200 s−1
Plug into the formula:
t1/2=200 s−10.693=0.003465 s
In scientific notation: 3.47×10−3 s.
When k is large, half-life is small — the reaction is fast. Here 200 s−1 means the reaction is over in milliseconds.
2. For k=2 min−1
t1/2=2 min−10.693=0.3465 min
That’s about 0.347 min, or roughly 20.8 seconds if you need it in seconds. …
Method: Half-Life Formula for First-Order Kinetics
For a first-order reaction, the half-life (t1/2) is independent of initial concentration and is given by:
t1/2=kln2=k0.693
Where:
- k = rate constant (must be in consistent time units)
- ln2≈0.693
Steps to Solve
- Identify the rate constant k and its units.
- Ensure time units are consistent — the half-life will have the same time unit as k.
- Substitute into t1/2=k0.693.
- Calculate and write the answer with correct units.
(i) k=200 s−1
t1/2=2000.693=0.003465 s
Answer: 3.47×10−3 s (or 3.47 ms)
(ii) k=2 min−1
t1/2=20.693=0.3465 min …
Here are the common mistakes students make when calculating half-life from rate constants in first-order kinetics, along with how to avoid each.
Mistake 1: Using the Wrong Formula
The Error
Students often confuse the half-life formula for first-order reactions with those for zero-order or second-order reactions. For a first-order reaction, the correct formula is:
t1/2=kln2=k0.693
Using t1/2=k1 or t1/2=k[A]01 is incorrect.
How to Avoid
- Memorise the formula with reasoning: The half-life for a first-order reaction is independent of initial concentration. Only k matters.
- Write the formula at the top of your solution before plugging in numbers.
Mistake 2: Ignoring Units of the Rate Constant
The Error
The rate constant k is given in different units: s−1, min−1, years−1. Students often forget to match the unit of t1/2 with the unit of k.
Example of the mistake:
For (ii) k=2 min−1, a student writes t1/2=20.693=0.3465 and leaves it unitless, or writes seconds instead of minutes.
How to Avoid
- Always write the unit of t1/2 explicitly.
- If k is in s−1, t1/2 is in seconds.
- If k is in min−1, t1/2 is in minutes.
- If k is in years−1, t1/2 is in years.
Correct answers:
- (i) t1/2=2000.693=3.465×10−3 s
- (ii) t1/2=20.693=0.3465 min
- (iii) t1/2=40.693=0.17325 years
Mistake 3: Rounding Off Too Early
The Error
Using 0.693 is standard, but some students round it to 0.7 or use 0.69 inconsistently, leading to slightly off answers. In competitive exams, precision matters.
How to Avoid
- Use 0.693 consistently (or ln2 if allowed).
- Do all calculations in one step on paper, then round only the final answer to 3–4 significant figures.
Mistake 4: Forgetting That Half-Life Is Independent of Initial Concentration
The Error
Some students try to find initial concentration [A]0 from the given data, or assume it is needed. This wastes time and can lead to wrong formulas.
How to Avoid
- Remember the key property: For a first-order reaction, t1/2 depends only on k. …
Showing the 12 most recent of 35 on this concept.
- AP EAPCET 2026Set eng-2026-05-12-FN1 markMCQQ.A(g)→ products, follows first order kinetics. Initial concentration of A is 8×10−3molL−1. For 80% decomposition of A, the time taken was 80 minutes. What is the rate constant for that reaction? (log 2 = 0.3, log 3 = 0.48, log 4 = 0.60, log 5 = 0.70) (A) 0.05 min−1 (B) 0.04 min−1 (C) 0.02 min−1 (D) 0.06 min−1
›Reveal solutionSolution
This tests the integrated first-order rate law; the answer is k≈0.02 min−1.
Concept and Intuition
For a first-order reaction, the rate constant only depends on the RATIO of initial to remaining concentration, not on the absolute concentration — this is why the initial concentration 8×10−3 mol/L given in the question is a distractor and isn't actually needed.
Step-by-Step Solution
- Integrated first-order equation: k=t2.303log[A]t[A]0.
- 80% decomposition means 80% of A is consumed, so 20% remains: [A]t=0.2[A]0, giving [A]t[A]0=0.21=5.
- Substitute t=80 min and log5=0.70 (given): k=802.303×0.70=801.6121.
- k≈0.02015 min−1≈0.02 min−1.
Common Mistakes …
- AP EAPCET 2026Set eng-2026-05-12-AN1 markMCQQ.At T(K), the following first order reaction takes place A(g)→B(g)+C(g) Initial pressure (t=0 min) of A(g) is pA0. After 10 min of the reaction, the pressure is pt. The correct equation for the rate constant of this reaction is (A) k=t1ln(2pA0−pt)pA0 (B) k=t2.303ln(2pA0−pt)pA0 (C) k=t2.303logpA0(2pA0−pt) (D) k=t1ln(3pA0−pt)pA0
›Reveal solutionSolution
Tracking total pressure for A→B+C shows the pressure of remaining A at time t is 2pA0−pt; substituting into the first-order rate law gives option (A).
Concept and Intuition
When a gas-phase reaction changes the number of moles, we can follow its progress via total pressure instead of concentration, since pressure is proportional to moles at constant volume/temperature. For A(g)→B(g)+C(g), every mole of A consumed produces one mole each of B and C — so the total moles (and hence total pressure) increase as the reaction proceeds, and this pressure change directly tells us how much A has reacted.
Step-by-Step Solution
- At t=0: only A present, pressure =pA0.
- At time t: let the pressure of A remaining be p. Then pressure of A reacted =pA0−p, and by stoichiometry, pressure of B formed =pA0−p and pressure of C formed =pA0−p (1:1:1 ratio).
- Total pressure: pt=p+(pA0−p)+(pA0−p)=2pA0−p
- Solve for p (pressure of A remaining): p=2pA0−pt …
- AP EAPCET 2026Set eng-2026-05-14-AN1 markMCQQ.Half-life of a first order reaction is 10 minutes. What is the rate of reaction after 20 minutes, if the initial concentration of the reactant is 10 M? (A) 1.73×10−1 M min−1 (B) 1.73×10−2 M min−1 (C) 3.46×10−1 M min−1 (D) 4.19×10−2 M min−1
›Reveal solutionSolution
After 2 half-lives the concentration drops to 2.5 M; the instantaneous first-order rate at that point is k[A]=1.73×10−1 M min⁻¹.
Concept and Intuition
For a first-order reaction, the rate constant is fixed by the half-life: k=0.693/t1/2, independent of concentration. The instantaneous rate at any time is rate=k[A]t, so we just need [A] at t=20 min.
Since 20 minutes equals exactly 2 half-lives (10 min each), the concentration halves twice.
Step-by-Step Solution
- k=0.693/10=0.0693 min−1.
- Number of half-lives elapsed in 20 min =20/10=2.
- [A]20=22[A]0=410=2.5 M. …
- AP EAPCET 2026Set eng-2026-05-15-FN1 markMCQQ.Hydrolysis of benzene diazonium chloride follows first order kinetics. The time taken for its decomposition to 81 and 101 of its original concentration are [t1/8] and [t1/10] respectively. What is the ratio of [t1/8] to [t1/10]? [log 2 = 0.30, log 3 = 0.48, log 4 = 0.60] (A) 9 : 10 (B) 10 : 9 (C) 3 : 5 (D) 5 : 3
›Reveal solutionSolution
For a first-order reaction, time to reach a given fraction remaining is proportional to log(C0/C); comparing log8 and log10 gives the required ratio. The answer is 9 : 10.
Concept and Intuition
For a first-order reaction, k=t2.303logCC0, so t=k2.303logCC0. Since k (the rate constant) is the same throughout for a given reaction at a given temperature, the time taken to reach any particular fraction of the original concentration is directly proportional to log(C0/C) for that fraction. This lets us compare two different "fraction remaining" times without ever needing to know k.
Step-by-Step Solution
- t1/8 is the time for concentration to fall to 1/8 of C0, i.e., C0/C=8: t1/8=k2.303log8.
- log8=log(23)=3log2=3×0.30=0.90. …
- AP EAPCET 2026Set ap-2026-05-20-AN1 markMCQQ.The time taken for 60% completion of a first order reaction is 13.22 min. What is its half-life (t1/2) in min? (log(2.5)=0.398) (A) 11 (B) 9 (C) 8 (D) 10
›Reveal solutionSolution
Using the first-order rate law with the given time for 60% completion, the half-life works out to 10 minutes.
Concept and Intuition
For first-order kinetics, the rate constant k can be found from any fraction reacted using k=t2.303log[A]t[A]0, and the half-life t1/2=k0.693 is independent of initial concentration — it only depends on k.
Step-by-Step Solution
- At 60% completion, 40% of the reactant remains: [A]t[A]0=40100=2.5.
- k=t2.303log(2.5)=13.222.303×0.398.
- Numerator =2.303×0.398=0.9166; so k=13.220.9166=0.0693 min−1. …
- AP EAPCET 2025Set eng-2025-05-21-FN1 markMCQQ.A → products, is a first order reaction. The following data is obtained for this reaction at T(K). The value of x : y is Rate (mol L−1 min−1) : [A] 0.2 : 0.02 M 0.4 : x M 1.0 : y M (A) 1 : 5 (B) 2 : 3 (C) 5 : 2 (D) 2 : 5
›Reveal solutionSolution
Tests the defining rate law of a first-order reaction, Rate =k[A]; the answer is (D) 2 : 5.
Concept and Intuition
For a first-order reaction A→products, the rate law is
Rate=k[A]
This means rate is directly proportional to concentration — double the concentration, double the rate. Since k is a constant at a fixed temperature T, every (Rate, [A]) pair in the table must give the same k. This lets us solve for the unknown concentrations x and y from the first data row.
Step-by-Step Solution
- Use the first row to find k: 0.2=k(0.02)⇒k=0.020.2=10 min−1.
- Apply the same k to row 2: 0.4=k⋅x=10x⇒x=0.04 M.
- Apply the same k to row 3: 1.0=k⋅y=10y⇒y=0.10 M. …
- AP EAPCET 2025Set eng-2025-05-22-AN1 markMCQQ.In a first order reaction, the concentration of the reactant is reduced to 1/8 of the initial concentration in 75 minutes. The t1/2 of the reaction (in minutes) is (log2=0.30, log3=0.47, log4=0.60) (A) 60.2 (B) 50.2 (C) 25.1 (D) 75.1
›Reveal solutionSolution
Falling to 1/8 of the initial concentration is exactly 3 half-lives (since 1/8=(1/2)3), so t1/2=75/3=25 min; using the given log values precisely gives 25.1 min. The answer is (C) 25.1 min.
Concept and Intuition
For a first-order reaction, the integrated rate law is
k=t2.303log[A][A]0
A defining feature of first-order kinetics is that the half-life t1/2=0.693/k is independent of concentration — each half-life always halves whatever concentration remains. So if the concentration falls to 81 of the original, that is exactly (21)3, meaning exactly 3 half-lives have elapsed.
Step-by-Step Solution
- Concentration ratio: [A]0/[A]=8.
- Since 8=23, note 1/8 of initial concentration corresponds to exactly 3 half-lives.
- Total time for 3 half-lives = 75 minutes, so one half-life t1/2=75/3=25 minutes (quick estimate).
- To match the precision implied by the given log values, compute via the rate constant: …
- AP EAPCET 2025Set ap-2025-05-19-FN1 markMCQQ.A→P is a first order reaction. At T(K), the concentration of reactant (A) after 10 min of the reaction is x molL−1. After 20 min of the reaction, the concentration of A was y molL−1. What is its rate constant (in min−1) ? (A) 0.2303logyx (B) 2.303logyx (C) 2.303logxy (D) 0.2303logxy
›Reveal solutionSolution
Using the first-order integrated rate law between t=10 min ([A]=x) and t=20 min ([A]=y), with Δt=10 min, gives k=0.2303log(x/y).
Concept and Intuition
For a first-order reaction A→P, the integrated rate law between any two times t1 and t2 (with concentrations C1 and C2) is
k=t2−t12.303logC2C1
This works between any two time points, not just from t=0, as long as the concentrations at those two times are known.
Step-by-Step Solution
- At t1=10 min, [A]=x. At t2=20 min, [A]=y.
- Time interval: Δt=t2−t1=10 min.
- k=Δt2.303logC2C1=102.303logyx.
- 102.303=0.2303.
- So k=0.2303logyx (in min−1).
Common Mistakes …
- AP EAPCET 2025Set ap-2025-05-20-AN1 markMCQQ.A→P is a first order reaction. The reaction was started at 10.00 AM. At 10.10 AM, the concentration of A was x mol L−1. At 10.20 AM, the concentration of A was y mol L−1. The half life (in min) of the reaction is equal to (A) log(x/y)2.303 (B) 3.01log(x/y) (C) log(y/x)3.01 (D) log(x/y)3.01
›Reveal solutionSolution
Since x and y are concentrations 10 minutes apart in a first-order reaction, the rate constant follows from the integrated rate law over that interval, giving t1/2=log(x/y)3.01.
Concept and Intuition
For a first-order reaction, the integrated rate law between any two times separated by Δt is
k=Δt2.303log[A]t2[A]t1
regardless of what the initial concentration was — because first-order kinetics only cares about the ratio of concentrations over the elapsed time, not the absolute starting point. This is why concentrations "10 minutes into the reaction" and "20 minutes into the reaction" can be treated as a self-contained 10-minute window.
Step-by-Step Solution
- From 10.00 AM to 10.10 AM to 10.20 AM, the interval between the two given concentrations is Δt=10 min.
- Apply the first-order integrated law over this window: k=102.303logyx.
- Half-life: t1/2=k0.693=2.303log(x/y)0.693×10. …
- AP EAPCET 2025Set eng-2025-05-24-FN1 markMCQQ.For a first order reaction, the ratio between the time taken to complete 43th of the reaction and time taken to complete half of the reaction is (A) 2 (B) 3 (C) 1.5 (D) 2.5
›Reveal solutionSolution
This tests the first-order rate law's independence from concentration; the ratio t3/4/t1/2=2 exactly.
Concept and Intuition
For a first-order reaction, the time to reach any fixed fraction of completion is a fixed multiple of the half-life, regardless of the starting concentration — this is the defining signature of first-order kinetics. Doubling the 'half-life count' needed (from one half-life to two half-lives) to go from 50% to 75% completion is exactly why the ratio comes out to a clean integer.
Step-by-Step Solution
- First-order integrated law: kt=ln[A]t[A]0.
- At t1/2: half of [A]0 remains, so kt1/2=ln[A]0/2[A]0=ln2.
- At t3/4: three-quarters consumed means one-quarter remains, so kt3/4=ln[A]0/4[A]0=ln4=2ln2. …
- AP EAPCET 2024Set ap-2024-05-16-FN1 markMCQQ.A→P is a first order reaction. At 27 °C, the time taken for the completion of 20 % of the reaction is t1 min. The time taken for the completion of 80 % of the reaction is t2 min at the same temperature. What is the value of t1t2? (log80=1.9; log20=1.3) (A) 71 (B) 7 (C) 73 (D) 14
›Reveal solutionSolution
Using the first-order rate law at 20% and 80% completion, the ratio t2/t1 reduces to log5/log1.25, which evaluates to 7 using the given log values.
Concept and Intuition
For a first-order reaction, the time to reach a given fraction of completion depends logarithmically on the fraction of reactant remaining: t=k2.303loga−xa. Taking the ratio of two such times eliminates the unknown rate constant k.
Step-by-Step Solution
- At 20% completion, 80% of a remains: t1=k2.303log80100=k2.303log(1.25).
- At 80% completion, 20% of a remains: t2=k2.303log20100=k2.303log(5).
- Ratio: t1t2=log1.25log5. …
- AP EAPCET 2024Set ap-2024-05-17-FN1 markMCQQ.At T(K), the decomposition of N2O5(g) is a first order reaction. The initial pressure of N2O5(g) is 'a' atm. After time, t, the total pressure of reaction is 'p' atm. The rate constant (k) of the reaction is (A) K=t1ln(a−2pa) (B) K=t1ln(3a−2p3a) (C) K=t1ln(3a−p3a) (D) K=21ln(5a−2p3a)
›Reveal solutionSolution
Tracking total pressure through the stoichiometry of
2N2O5→4NO2+O2 shows the remaining
N2O5 pressure is 35a−2p, giving the first-order rate constant
the form in option (D).
Concept and Intuition
This is the standard "gas-phase first-order decomposition tracked by total pressure"
problem. Because the number of moles of gas changes during the reaction, the total
pressure p at time t is NOT simply the pressure of unreacted N2O5 — you
must use the reaction stoichiometry to relate the increase in total pressure to how
much N2O5 has actually decomposed, then plug the leftover N2O5
pressure into the first-order integrated rate law k=t1ln[A]t[A]0.
Step-by-Step Solution
- Reaction: 2N2O5(g)→4NO2(g)+O2(g).
- Let 2ξ = pressure of N2O5 consumed. By stoichiometry, NO2 formed =4ξ and O2 formed =ξ.
- Species pressures at time t: N2O5=a−2ξ, NO2=4ξ, O2=ξ.
- Total pressure: p=(a−2ξ)+4ξ+ξ=a+3ξ⇒ξ=3p−a.
- Remaining N2O5=a−2ξ=a−32(p−a)=33a−2p+2a=35a−2p. …
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