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
Showing the 12 most recent of 26 on this concept.
- CBSE 2026Set 56/1/11 markMCQQ.Which of the following curve represents the first order reaction ? (A) A graph of t1/2 (y-axis) against initial concentration [R]0 (x-axis): a straight line rising from the origin (B) A graph of t1/2 against [R]0: a horizontal straight line (t1/2 independent of [R]0) (C) A graph of Rate against Concentration: a horizontal straight line (D) A graph of Rate against Concentration: a curve that falls as concentration increases
›Reveal solutionSolution
For a first-order reaction, the half-life t1/2 is independent of the initial concentration [R]0, so the correct plot is a horizontal straight line on a t1/2 vs. [R]0 graph — option (B).
The key to this question is knowing how the half-life of a reaction depends on the initial concentration — and that dependence is different for different orders. Let’s build the intuition from the Arrhenius equation and the integrated rate laws.
Why this approach works
For a first-order reaction, the rate law is:
Rate=k[R]
where k is the rate constant. The integrated form gives:
ln[R][R]0=kt
The half-life t1/2 is the time when [R]=2[R]0. Substituting:
ln[R]0/2[R]0=kt1/2⇒ln2=kt1/2
So:
t1/2=kln2
Notice: no [R]0 appears in this expression. That’s the defining feature — for a first-order reaction, the half-life is a constant, determined only by the rate constant k.
Now let’s examine each option.
-
Option (A): A straight line rising from the origin on a t1/2 vs. [R]0 graph. This would mean t1/2∝[R]0, which is true for a zero-order reaction (where t1/2=[R]0/2k). Not first-order.
-
Option (B): A horizontal straight line — t1/2 does not change as [R]0 changes. This matches t1/2=ln2/k, a constant. This is the correct plot for a first-order reaction.
-
Option (C): A graph of Rate vs. Concentration that is a horizontal straight line. That would mean Rate is independent of concentration — which is true for a zero-order reaction (Rate = k). For first-order, Rate = k[R], so the plot is a straight line through the origin, not horizontal.
-
Option (D): A Rate vs. Concentration curve that falls as concentration increases. This would imply a negative order or some complex kinetics — not first-order. For first-order, rate increases linearly with concentration.
Watch outA common mistake is to confuse the half-life plot with the rate vs. concentration plot. For first-order, the rate increases with concentration (linear), but the half-life is constant. These are different graphs — don’t mix them up.
TipMemorise the half-life dependence for each order as a quick check:
- Zero-order: t1/2∝[R]0 (rising line)
- First-order: t1/2 constant (horizontal line)
- Second-order: t1/2∝1/[R]0 (falling curve)
✓Final answerThe correct option is (B).
-
- CBSE 2026Set A1 markMCQQ.Which of the following is not a first order reaction ?(a) CH3COOC2H5 + H2O --(H+)--> CH3COOH + C2H5OH(b) CH3COOC2H5 + NaOH --> CH3COONa + C2H5OH(c) 2H2O2 --> 2H2O + O2(d) 2N2O5 --> 4NO2 + O2
›Reveal solutionSolution
Ester hydrolysis by NaOH (saponification) is second order (first order in ester and first order in OH-), so it is NOT a first-order reaction.
-
(a) Acid hydrolysis of ester with excess water is pseudo-first order.
-
(b) Alkaline hydrolysis (saponification) with NaOH: rate = k[ester][OH-], overall second order — this is not first order.
-
(c) Decomposition of H2O2 is first order.
-
(d) Decomposition of N2O5 is first order.
✓Final answer(b) CH3COOC2H5 + NaOH → CH3COONa + C2H5OH.
-
- CBSE 2026Set ANNUAL1 markMCQQ.Acid hydrolysis of ethyl acetate is:(a) Zero order reaction(b) First order reaction(c) Second order reaction(d) Third order reaction
›Reveal solutionSolution
Acid hydrolysis of ethyl acetate is a classic example of a pseudo first order reaction.
The reaction is: CH3COOC2H5+H2OH+CH3COOH+C2H5OH. Strictly, this reaction depends on the concentrations of BOTH the ester and water, and should be second order overall (first order in each). However, water is used as the solvent and is present in vast molar excess compared to the ester, so as the reaction proceeds its concentration barely changes and can be treated as effectively constant.
Under this condition, the rate law Rate=k′[ester][H2O] simplifies to Rate=k[ester] (where k=k′[H2O] is an apparent/pseudo rate constant), and the reaction follows first-order kinetics experimentally even though it is truly bimolecular (second order) in mechanism. This is why it is termed a "pseudo first order" reaction — kinetically it behaves as first order.
✓Final answer(b) It is (pseudo) first order reaction with respect to the ester, since water is in large excess.
- CBSE 2026Set ANNUAL1 markMCQQ.The value of rate constant of a pseudo-first-order reaction(a) depends on the concentration of reactants present in small amount(b) depends on the concentration of reactants present in excess(c) is independent of the concentration of the reaction(d) depends only on temperature
›Reveal solutionSolution
A pseudo-first-order rate constant is not a true elementary-step constant — it already has the (essentially fixed) concentration of the reactant present in excess multiplied into it, so its numerical value depends on how much of that excess reactant was used.
Example — acid-catalysed hydrolysis of ethyl acetate:
CH3COOC2H5+H2OH+CH3COOH+C2H5OH
The true rate law is rate=k[ester][H2O]. Since water is the solvent and is present in huge excess, [H2O] stays essentially constant throughout the reaction, so rate=k′[ester] where k′=k[H2O]. Experimentally the reaction looks first order (only [ester] appears), but the measured k′ is really the true rate constant k multiplied by whatever fixed [H2O] happened to be present.
Why the other options are wrong:
-
(a) It is the concentration of the reactant present in excess — not the one present in a small amount — that gets folded into kobs.
-
(c) kobs is not independent of concentration; it explicitly carries the excess reactant's concentration inside it.
-
(d) True rate constants do depend on temperature too, but that is a separate, general fact about all rate constants — it does not capture what is distinctively 'pseudo' about a pseudo-first-order constant, which is its dependence on the excess reactant's concentration.
✓Final answer(b) depends on the concentration of the reactant(s) present in excess
-
- CBSE 2025Set 56/6/11 markMCQQ.For the following question, two statements are given — one labelled as Assertion (A) and the other labelled as Reason (R). Select the correct answer from the codes (A), (B), (C) and (D) as given below. (A) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A). (B) Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of the Assertion (A). (C) Assertion (A) is true, but Reason (R) is false. (D) Assertion (A) is false, but Reason (R) is true. Assertion (A) : Hydrolysis of an ester follows first order kinetics. Reason (R) : The concentration of water does not get altered much during the reaction.
›Reveal solutionSolution
The assertion is true because ester hydrolysis is pseudo-first order; the reason correctly explains why — water is in large excess so its concentration stays nearly constant, making the observed kinetics first order.
The Concept: Why First Order Kinetics Appears
When you study reaction kinetics, the order of a reaction tells you how the rate depends on the concentrations of reactants. For a true bimolecular reaction like ester hydrolysis:
CH3COOC2H5+H2OH+CH3COOH+C2H5OH
The rate law should be:
Rate=k[ester][H2O]
That would make it second order overall — first order in ester and first order in water. But here’s the twist: in practice, the reaction is carried out in aqueous solution where water is the solvent. Its concentration is about 55.5 M, while the ester concentration is typically 0.1 M or less. So water is in huge excess.
TipWhen one reactant is present in such large excess that its concentration changes negligibly during the reaction, we can treat it as constant. The rate law then appears to depend only on the other reactant — this is called pseudo-first order kinetics.
Since [H2O] remains essentially constant, we absorb it into the rate constant:
Rate=k′[ester],where k′=k[H2O]
This is exactly the form of a first order reaction. So the assertion is correct — hydrolysis of an ester follows first order kinetics (under typical conditions).
Step-by-Step Reasoning
-
Identify the true order of the reaction.
The balanced equation shows one molecule of ester reacts with one molecule of water. The fundamental rate law is second order: Rate=k[ester][H2O].
-
Examine the reaction conditions.
In a typical lab or exam context, ester hydrolysis is done in dilute aqueous solution. Water is the solvent — its initial concentration is ~55.5 M and it barely changes because only a tiny fraction is consumed.
-
Apply the concept of excess reactant.
Because [H2O] is so large and its change is negligible, we treat it as a constant. The rate law simplifies to Rate=(k[H2O])[ester]=kobs[ester].
-
Recognise the kinetic order.
A rate law of the form Rate=kobs[ester] is first order. The integrated form gives ln[ester]t=ln[ester]0−kobst, which is the hallmark of first order decay.
-
Evaluate the reason statement.
The reason says: "The concentration of water does not get altered much during the reaction." This is exactly why the kinetics become pseudo-first order. Without this fact, the reaction would be second order. So the reason is true and it correctly explains the assertion.
Watch outA common mistake is to think ester hydrolysis is truly first order. It is not — it is pseudo-first order. The reason is crucial: without the excess water condition, the assertion would be false.
Final Answer
✓Final answerBoth Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A). The correct option is (A).
-
- CBSE 2025Set X11 markMCQQ.An example for pseudo first-order reaction is,(a) The decomposition of gaseous ammonia on a hot platinum surface(b) Photochemical reaction between hydrogen and chlorine(c) Inversion of cane sugar(d) Hydrogenation of ethene
›Reveal solutionSolution
Inversion (hydrolysis) of cane sugar is the standard example of a pseudo first-order reaction — water is in large excess so its concentration is effectively constant.
Hydrolysis of sucrose (cane sugar) into glucose and fructose:
sucroseC12H22O11+H2OH+glucoseC6H12O6+fructoseC6H12O6
The true rate law is rate=k[sucrose][H2O] (second order). But water is present in very large excess, so [H2O] is essentially constant, and the rate becomes rate=k′[sucrose] — first order in practice. Such a reaction is called pseudo first-order. This is the classic textbook example.
✓Final answer(c) Inversion of cane sugar
- CBSE 2025Set A1 markQ.Fill in the blank: The unit of a first order rate constant is ______.
›Reveal solutionSolution
A first-order rate constant always has the unit of (time)⁻¹, e.g. s⁻¹.
For a reaction of order n, the rate constant k has general units of (mol L−1)1−ntime−1. For a first-order reaction (n=1), the concentration term's exponent becomes zero, so the concentration unit cancels out completely, leaving only:
k=t1ln[A]t[A]0⇒unit of k=time−1=s−1
This is a useful diagnostic — if a rate constant's unit works out to be independent of concentration (pure s⁻¹, min⁻¹, etc.), the reaction is first order.
✓Final answers⁻¹ (time⁻¹).
- CBSE 2025Set ANNUAL1 markMCQQ.What is the concentration of the reactant in a first order reaction, when the rate of the reaction is 0.6 Ms^-1 and the rate constant is 0.035 s^-1 ?(a) 26.667 M(b) 17.143 M(c) 26.183 M(d) 17.667 M
›Reveal solutionSolution
For a first order reaction, Rate = k[R], so the reactant concentration is simply Rate divided by the rate constant.
For a first order reaction:
Rate=k[R]
[R]=kRate=0.035 s−10.6 M s−1=17.142857... M≈17.143 M
✓Final answer(b) 17.143 M.
- CBSE 2025Set ANNUAL1 markMCQQ.The units of first order reaction:(a) s⁻¹(b) s(c) mol L⁻¹(d) L⁻¹s
›Reveal solutionSolution
The rate constant of a first order reaction has units of (time)⁻¹, i.e. s⁻¹.
For a general reaction of order n, rate =k[A]n, so
k=[A]nrate=(molL−1)nmolL−1s−1
For a first order reaction (n=1):
k=molL−1molL−1s−1=s−1
The concentration units cancel out completely, leaving only inverse time.
✓Final answer(a) s⁻¹
- CBSE 2025Set ANNUAL1 markMCQQ.Which one of the following is a pseudo first order reaction?(a) Hydrogenation of ethene(b) Hydrolysis of ethyl acetate in the presence of dilute acid(c) Combination of H2 and Br2(d) Decomposition of NH2 on a platinum surface
›Reveal solutionSolution
Water, present in huge excess as solvent, has an essentially constant concentration during the ester's hydrolysis, so the true second-order rate law collapses to an apparent first-order one.
The acid-catalyzed hydrolysis CH₃COOC₂H₅ + H₂O → CH₃COOH + C₂H₅OH is genuinely second order overall (first order in ester, first order in water), but since water is present in vast excess (it is essentially the solvent), its concentration barely changes during the reaction and gets absorbed into the rate constant, so the reaction experimentally behaves as first order — a pseudo first order reaction. (Hydrogenation of ethene and the H₂+Br₂ combination are genuinely second order; decomposition of NH₃ on a Pt surface is a genuine zero order reaction.)
✓Final answer(b) Hydrolysis of ethyl acetate in the presence of dilute acid.
- CBSE 2024Set ANNUAL1 markMCQQ.The unit of rate constant for a first order reaction is -(a) L2Sec−1(b) Sec−1(c) MolL−1Sec−1(d) Mol−1LSec−1
›Reveal solutionSolution
A first order rate constant has units of (time)−1.
For a reaction of order n, the rate constant k has units of (concentration)1−n(time)−1. For a first order reaction, n=1, so the concentration term cancels out ((concentration)1−1=(concentration)0=1) and only the time term remains:
k=Sec−1
✓Final answer(ii) Sec−1
- CBSE 2024Set D1 markMCQQ.Which of the following is not a first order reaction?(a) CH3COOCH3 + H2O --H+--> CH3COOH + CH3OH(b) CH3COOC2H5 + NaOH -> CH3COONa + C2H5OH(c) 2H2O2 -> 2H2O + O2(d) 2N2O5 -> 4NO2 + O2
›Reveal solutionSolution
Saponification of an ester by NaOH is second order; the other three are (pseudo/) first order.
- (a) Acid hydrolysis of an ester (with H+ and large excess water) is a pseudo-FIRST-order reaction.
- (b) Ester + NaOH (saponification) depends on both [ester] and [OH-], so rate = k[ester][OH-]: SECOND order.
- (c) Decomposition of H2O2 (2H2O2 -> 2H2O + O2) is first order.
- (d) Decomposition of N2O5 (2N2O5 -> 4NO2 + O2) is a classic first-order reaction.
Hence (b) is not first order.
✓Final answer(b) CH3COOC2H5 + NaOH -> CH3COONa + C2H5OH — a second-order reaction.
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