Q.A first order reaction has a rate constant 1.15×10−3 s−1. How long will 5 g of this reactant take to reduce to 3 g?
Concept understanding — First Order Kinetics
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.
- Drug elimination from the body: Many drugs are cleared from the bloodstream by first order processes. A fixed fraction of the drug is eliminated per unit time, not a fixed amount.
- Hydrolysis of esters: In excess water, the reaction appears first order with respect to the ester.
A common mistake: thinking that "first order" means the reaction happens in one step. It does not. Order is an empirical quantity determined by experiment, not by the reaction mechanism. A reaction can be first order overall even if it involves multiple elementary steps.
Summary
First order kinetics describes processes where the rate is proportional to the amount remaining. The concentration decays exponentially, and the half-life is constant. It's one of the most fundamental and widely applicable concepts in chemical kinetics — and once you see the exponential decay pattern, you'll spot it everywhere.
First order kinetics is one of the most numerically tested topics in the NCERT/CBSE Class 12 Chemistry Chemical Kinetics chapter, and ‘first order reaction formula’ or ‘first order kinetics half life’ are among the top important-question searches for board exams, JEE Main and NEET. Its constant half-life property is a key fact examined repeatedly in competitive-exam chemistry numericals.
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)
From ln[A]t=ln[A]0−kt:
- Plot ln[A]t vs t → straight line
- Slope = −k
- Intercept = ln[A]0
Why this matters: If your experimental data gives a straight line on a ln[A] vs time plot, the reaction is first order. This is how you identify the order experimentally.
Summary of Key Results
| Quantity | Formula | Why? |
|---|---|---|
| Rate law | −dtd[A]=k[A] | Rate ∝ concentration of one reactant |
| Integrated form | ln[A]t=ln[A]0−kt | From integration of rate law |
| Exponential form | [A]t=[A]0e−kt | Antilog of integrated form |
| Half-life | t1/2=kln2 | Constant, independent of [A]0 |
Final takeaway: First order kinetics is exponential decay driven by a constant probability of reaction per molecule per unit time. The formulas are not arbitrary — they follow directly from this simple assumption.
The key idea is First Order Kinetics, where the rate depends only on the concentration of one reactant. For a first order reaction, the integrated rate law relates time, the rate constant k, and the ratio of initial and remaining amounts.
Step 1: Write the integrated first order rate law in terms of mass (since mass is proportional to concentration for a given volume):
t=k2.303log[A][A]0
Step 2: Substitute the given values. Initial mass [A]0=5 g, remaining mass [A]=3 g, and k=1.15×10−3 s−1:
t=1.15×10−32.303log35
Step 3: Calculate log(5/3)=log(1.6667)≈0.2218. Then:
t=1.15×10−32.303×0.2218=2000×0.2218≈443.6 s
The time required is 444 s (approximately).
For a first-order reaction, the time required for a concentration change depends only on the rate constant and the ratio of initial to final amounts — not on the absolute mass. Using the integrated rate law, the time for 5 g to reduce to 3 g is 444 s.
First-order kinetics is one of the simplest and most elegant rate laws in chemistry. The defining property: the rate of reaction is directly proportional to the concentration (or amount) of a single reactant. This means that in equal time intervals, the fraction of reactant remaining is constant — not the absolute amount lost.
Why does that matter here? Because we’re given masses (5 g and 3 g), not concentrations. But for a first-order reaction, the ratio of amounts at two times is all we need. The volume cancels if the reaction is in solution, and if it’s a pure solid decomposing, the mass is directly proportional to the number of moles. So we can treat mass as a proxy for concentration.
The integrated rate law for a first-order reaction is:
ln[A]t[A]0=kt
where [A]0 is the initial concentration (or amount), [A]t is the concentration at time t, and k is the rate constant.
We want t, so rearrange:
t=k1ln[A]t[A]0
Now plug in the numbers.
-
Identify the given values.
k=1.15×10−3 s−1
Initial mass m0=5 g
Final mass mt=3 g
Since mass is proportional to amount for a pure substance, [A]t[A]0=mtm0=35.
-
Write the expression for time.
t=1.15×10−31ln(35)
-
Compute the natural logarithm.
35≈1.6667
ln(1.6667)≈0.5108
(You can verify: e0.5108≈1.667.)
-
Divide by the rate constant.
t=1.15×10−30.5108=0.001150.5108
Do the division:
0.5108÷0.00115=444.17 s.
- Round appropriately. The rate constant is given to three significant figures, so the time should be reported to three significant figures as well: 444 s.
A common mistake is to use ln[A]0[A]t instead of [A]t[A]0. That gives a negative time — which is nonsense. Always check: if the amount decreases, the ratio [A]t[A]0>1, so ln is positive.
You can also solve using the half-life formula: t1/2=kln2≈603 s. Then note that 5 g → 3 g is not a half-life (which would be 2.5 g), but you can still use the fraction-remaining approach. The direct log method is faster here.
The time required is 444 s.
Method: Integrated Rate Law for First-Order Kinetics
For a first-order reaction, the rate depends linearly on the concentration of one reactant. The key relationship is:
ln[A]t[A]0=kt
Where:
- [A]0 = initial concentration (or amount)
- [A]t = concentration (or amount) at time t
- k = rate constant
- t = time
Since mass is proportional to concentration (same volume), we can directly use masses.
Steps
-
Identify given data
- k=1.15×10−3 s−1
- Initial mass =5 g
- Final mass =3 g
-
Write the integrated rate law with masses
ln35=kt
- Solve for t
t=kln(5/3)
- Calculate
- ln(5/3)=ln(1.6667)≈0.5108
- t=1.15×10−30.5108
t≈444.2 s
Final Answer:
444 s (approximately)
Key insight: In first-order kinetics, the time depends only on the ratio of initial to remaining amount — not on the absolute quantity. That’s why we used grams directly.
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 (Zero Order or Second Order)
The error:
Students often plug numbers into the zero-order equation (t=k[A]0−[A]) or the second-order equation (t=k1([A]1−[A]01)) because they memorise formulas without checking the order.
Why it happens:
The problem explicitly says “first order reaction,” but under time pressure, students grab the first formula they recall.
How to avoid:
- Always confirm the order from the question before writing any equation.
- For first order, the integrated rate law is:
t=k2.303log[A][A]0
- Write this formula down before substituting numbers.
Mistake 2: Confusing mass with concentration
The error:
Students think they need to convert 5 g and 3 g into molar concentrations (mol/L) using molar mass and volume.
Why it happens:
Textbook problems often use concentration (mol/L), so students assume mass cannot be used directly.
How to avoid:
- For a first order reaction, the ratio [A][A]0 is dimensionless.
- Since mass is directly proportional to concentration (same volume, same container), you can use mass in grams directly:
[A][A]0=3 g5 g
- No need for molar mass or volume — just the ratio of initial to remaining mass.
Mistake 3: Using log instead of log10 (or vice versa)
The error:
Students use natural log (ln) with the constant 2.303, or use log10 without the 2.303 factor.
Why it happens:
The formula t=k2.303log[A][A]0 uses base-10 log. Some calculators default to ln.
How to avoid:
- Remember:
lnx=2.303log10x
- If your calculator has only ln, compute ln(5/3) and then divide by 2.303 to get log10(5/3).
- Better: use the log button (base 10) directly.
Mistake 4: Forgetting to match time units with k
The error:
The rate constant k=1.15×10−3 s−1 is in s−1, but students report the answer in minutes or hours without converting.
Why it happens:
They compute t in seconds but then write “444 s” as the final answer without checking if the question expects a different unit.
How to avoid:
- Always check the unit of k — here it’s s−1, so t will be in seconds.
- If the question asks for minutes or hours, convert at the end:
minutes=60seconds
hours=3600seconds
Mistake 5: Arithmetic errors in the log calculation
The error:
Students compute 35=1.6667, then take log(1.6667)≈0.2218, but then multiply/divide incorrectly.
Why it happens:
Rushing through calculator steps or misplacing decimal points.
How to avoid:
- Write the calculation step-by-step:
t=1.15×10−32.303×log(35)
- First compute 1.15×10−32.303=2002.6 (approx).
- Then log(5/3)≈0.2218.
- Multiply: 2002.6×0.2218≈444 s.
Double-check with estimation:
- 0.001152.303≈2000
- log(1.67)≈0.22
- 2000×0.22=440 s — so 444 s is reasonable.
Quick Summary Checklist
| Mistake | How to Avoid |
|---|---|
| Wrong formula | Write first-order formula first |
| Mass vs concentration | Use mass ratio directly |
| Log base error | Use log10 with 2.303 |
| Unit mismatch | Keep k unit → time unit |
| Arithmetic slip | Estimate before calculating |
Final answer (for reference):
t=1.15×10−32.303log(35)≈444 s
- 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.
- [P], the product concentration, INCREASES with time and levels off. Option (C) shows [P] DECREASING with time, which is incorrect.
Only Option (A) correctly represents first-order kinetics.
[!ANSWER] The correct graph is Option (A): log([R]0/[R]) versus Time is a straight line rising from the origin with positive slope.
ANSWER: (A)
Option A: y-axis log([R]0/[R]), x-axis Time - a straight line starting at the origin and r - 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.
Comparing with y=(slope)t, the plot of y=log[R][R]0 versus t is linear through the origin with slope 2.303k. Option (B) would give slope −k/2.303; options (C) and (D) use natural log so their slopes are +k and −k respectively.
[!ANSWER]
(A) log[R][R]0 vs t
- 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
Plotting log[R][R]0 (y) against t (x) gives a straight line through the origin with slope 2.303K (positive, since the LHS grows with time).
✓Final answer(B) 2.303K.
ANSWER: (B)
- 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
Plotting log[R][R]0 versus t gives a straight line through the origin with slope 2.303k (positive).
✓Final answer(A) 2.303K
ANSWER: (A)
- 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
Reducing to 161=(21)4 needs 4 half-lives:
t=4×0.01155=0.0462≈4.6×10−2 s
✓Final answer(C) 4.6×10−2
ANSWER: (C)
- 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:
k=24000.693=2.888×10−4s−1.
✓Final answer(A) 2.88×10−4s−1
ANSWER: (A)
- 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, where t1/2∝1/[A]0.)
Solution
Since t1/2=0.693/k has no dependence on [A]0, the half-life period of a first-order reaction is independent of concentration.
[!ANSWER] (B)
- 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
Reducing concentration to 101th means [A][A]0=10, so log10=1.
t=k2.303×1=2.303×10−22.303=102=100 s
[!ANSWER]
(B) 100 second
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