Q.The rate constant for a first order reaction is 60 s−1. How much time will it take to reduce the initial concentration of the reactant to its 1/16th value?
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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) …
The key idea is First Order Kinetics, where the integrated rate law relates concentration to time:
t=k2.303log[A][A]0.
Step 1: The concentration is reduced to 161 of its initial value, so
[A][A]0=16.
Step 2: Substitute k=60 s−1 into the formula:
t=602.303log16.
Step 3: log16=log24=4log2≈4×0.3010=1.204. …
For a first-order reaction, the time to reduce concentration to 1/16th is four half-lives. Since t1/2=kln2=60 s−10.693≈0.01155 s, the required time is 4×0.01155=0.0462 s.
First-order kinetics is one of the cleanest models in chemical kinetics because the rate depends only on the concentration of one reactant. The key insight: the time to go from any concentration to a fraction of it is constant — that’s the half-life property. For a first-order reaction, each half-life reduces the concentration by half. So if you want to go from [A]0 to [A]0/16, you’re asking: how many half-lives does it take to drop to 1/16th?
1/16=(1/2)4, so it takes exactly 4 half-lives. That’s the conceptual shortcut. But let’s verify it formally using the integrated rate law, because exams often test both the formula and the reasoning.
- Write the integrated rate law for a first-order reaction. The standard form is:
ln[A][A]0=kt
where [A]0 is the initial concentration, [A] is the concentration at time t, and k is the rate constant.
- Plug in the given fraction. We want [A]=16[A]0. So:
ln[A]0/16[A]0=ln16=kt
- Simplify ln16. 16=24, so ln16=4ln2. Thus:
4ln2=kt
- Solve for t.
t=k4ln2
- Substitute k=60 s−1. Using ln2≈0.693: …
Method: Integrated Rate Law for First-Order Reactions
This is the standard approach for solving time–concentration problems in first-order kinetics.
Steps
- Recall the integrated rate law For a first-order reaction:
k=t2.303log[A]t[A]0
where
- k = rate constant (60 s−1)
- [A]0 = initial concentration
- [A]t = concentration at time t
- Identify the given ratio The concentration is reduced to 161 of its initial value:
[A]0[A]t=161
Therefore:
[A]t[A]0=16
- Substitute into the equation
60=t2.303log16
- Simplify the logarithm
log16=log(24)=4log2
Using log2≈0.3010:
log16=4×0.3010=1.204
- Solve for t
t=602.303×1.204
t=602.773
t≈0.0462 s
Quick Check (Alternative Method) …
Here are the most common mistakes students make when solving this first-order kinetics problem, along with how to avoid each.
Mistake 1: Using the wrong formula for the number of half-lives
Students often try to use the half-life formula directly without checking if the fraction 1/16 is a simple power of 1/2.
- The error: They might calculate t1/2=k0.693 and then multiply by 4 (since 1/16=(1/2)4). This is actually correct for this specific fraction, but the mistake is doing this blindly without verifying the fraction is a power of 1/2.
- How to avoid: Always check: 1/16=(1/2)4 → 4 half-lives. Then t=4×t1/2=4×60 s−10.693.
- Key insight: This shortcut only works when the fraction is exactly (1/2)n. For fractions like 1/10 or 1/3, you must use the integrated rate law.
Mistake 2: Forgetting to convert units or misplacing the rate constant
The rate constant is given as 60 s−1. Some students treat it as if it were in minutes or hours, or they incorrectly invert it.
- The error: Writing t=k2.303log[A][A]0 but then plugging k=60 without checking units, or writing t=600.693 and forgetting the unit is seconds.
- How to avoid:
- Always write the unit alongside the number: k=60 s−1.
- The answer will be in seconds (since k is in s−1).
- If the question expects an answer in minutes, convert at the end: divide by 60.
Mistake 3: Using the wrong logarithm base in the integrated rate law
The first-order integrated rate law is:
t=k2.303log10[A][A]0
Some students use natural log (ln) but forget the factor 2.303, or they use log10 but omit the 2.303.
- The error: Writing t=k1ln[A][A]0 (correct) but then using log10 tables without converting, or writing t=k1log10[A][A]0 (wrong).
- How to avoid:
- Stick to one form and be consistent.
- If using ln: t=k1ln[A][A]0
- If using log10: t=k2.303log10[A][A]0
- For this problem, since [A]0/[A]=16, log1016=1.2041 and ln16=2.7726. Both give the same t if you use the correct factor.
Mistake 4: Misidentifying the ratio [A]0/[A]
Students sometimes invert the fraction.
- The error: They set [A][A]0=161 instead of 16.
- How to avoid: The question says "reduce to its 1/16th value". So [A]=161[A]0. Therefore [A][A]0=161[A]0[A]0=16. Always write it out: final concentration = initial concentration divided by 16.
Mistake 5: Arithmetic errors in the final calculation …
- GUJCET 2024Set 131 markMCQQ.Which of the following graphs is correct for a first order reaction R→P? [FIGURE: four plots] (A) [FIGURE] Plot of log[R][R]0 (y-axis) versus Time (x-axis): a straight line rising from the origin with positive slope (B) [FIGURE] Plot of t1/2 (y-axis) versus [R]0 (x-axis): a straight line with negative slope (decreasing) (C) [FIGURE] Plot of molar concentration [P] (y-axis) versus Time (x-axis): a curve decreasing and levelling off (D) [FIGURE] Plot of t1/2 (y-axis) versus [R]0 (x-axis): a straight line rising from the origin (increasing)
›Reveal solutionSolution
[!TLDR] For a first-order reaction the integrated rate law gives log([R]0/[R]) = (k/2.303)*t, a straight line through the origin with positive slope - Option (A).
For a first-order reaction R -> P, the integrated rate law is ln([R]0/[R]) = k*t, i.e. log([R]0/[R]) = (k/2.303)*t. This is a straight line passing through the origin with a constant positive slope of k/2.303 when plotted against time - exactly what Option (A) shows.
Check the other options:
- Half-life of a first-order reaction, t(1/2) = 0.693/k, is INDEPENDENT of [R]0, so a plot of t(1/2) vs [R]0 must be a horizontal line. Option (B) shows a decreasing line (characteristic of second order) and Option (D) shows a rising line through the origin (characteristic of zero order) - both wrong. …
- GUJCET 2023Set 091 markMCQQ.For which of the following graph of first order reaction the value of slope will be 2.303K? (A) log[R][R]0→t(Time) (B) log[R]0[R]→t(Time) (C) ln[R][R]0→t(Time) (D) ln[R]0[R]→t(Time)
›Reveal solutionSolution
[!TLDR]
Rearranging the first-order integrated law gives a straight line of slope k/2.303 when log([R]0/[R]) is plotted against time.
Concept
For a first-order reaction, the integrated rate equation is k=t2.303log[R][R]0.
Solution
Rearrange:
log[R][R]0=2.303kt. …
- GUJCET 2022Set 171 markMCQQ.What is the value of slope when graph plotted of log[R][R]0 Vs t (time) for first order reaction? (A) −2.303K (B) 2.303K (C) −K (D) K2.303
›Reveal solutionSolution
Slope =2.303K.
Concept. Integrated first-order law:
log[R][R]0=2.303Kt …
- GUJCET 2021Set 151 markMCQQ.For first order reaction, the value of slope for graph of log[R][R]0→t is ___. (A) 2.303K (B) K2.303 (C) −K (D) −2.303K
›Reveal solutionSolution
Integrated first-order law in log form has slope =2.303k.
Concept: For first order, ln[R][R]0=kt. Converting to base-10 log:
log[R][R]0=2.303kt …
- GUJCET 2021Set 151 markMCQQ.The rate constant for a first order reaction is 60 s−1. How much second will it take to reduce the initial concentration of the reactant to its 161th value? (A) 2.3×10−2 (B) 9.5×10−2 (C) 4.6×10−2 (D) 6.9×10−2
›Reveal solutionSolution
1/16=(1/2)4 → 4 half-lives → t≈4.6×10−2 s.
Concept: For first order, t1/2=k0.693, and each half-life halves the concentration.
t1/2=600.693=0.01155 s …
- GUJCET 2020Set 071 markMCQQ.Time required to decompose SO2Cl2 to half of its initial amount is 40 minutes. If the decomposition is a first order reaction, What will be the rate constant of the reaction? (A) 2.88×10−4s−1 (B) 2.88×10−2s−1 (C) 1.73×10−2s−1 (D) 1.73×10−4s−1
›Reveal solutionSolution
k=t1/20.693=2400s0.693=2.88×10−4s−1.
Concept — first-order half-life. For first order t1/2=0.693/k. With t1/2=40 min =2400 s: …
- GUJCET 2014Set A1 markMCQQ.The half life period for a first order reaction is __________. (A) Proportional to concentration (B) Independent of concentration (C) Inversely proportional to concentration (D) Inversely proportional to the square of the concentration
›Reveal solutionSolution
[!TLDR] First-order half-life t1/2=0.693/k is independent of the starting concentration.
Concept
For a first-order reaction, the integrated rate law gives t1/2=kln2=k0.693. Because k is a constant at a given temperature and no concentration term appears, the half-life is fixed regardless of how much reactant you begin with. (Contrast with a zero-order reaction, where t1/2∝[A]0, and second-order, whe …
- GUJCET 2014Set A1 markMCQQ.The value of rate constant for a first order reaction is 2.303×10−2 sec−1. What will be the time required to reduce the concentration to 101th of its initial concentration? (A) 10 second (B) 100 second (C) 2303 second (D) 230.3 second
›Reveal solutionSolution
[!TLDR]
First-order kinetics: t=100 s.
Concept
The integrated first-order rate law is k=t2.303log[A][A]0, i.e. t=k2.303log[A][A]0 (NCERT Chemical Kinetics).
Solution …
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