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NEET 2027 · Chemistry · Chemical Kinetics · Topic 01 of 15

First Order Rate Law
& Half-Life

Tier 1 · highest priority. The single most-asked unit in the chapter — concepts from the ground up, four animations, a complete formula sheet, and 76 worked questions.

Tier · 1 — HighestNCERT · §3.3.2 · §3.3.3Animations · 4Questions · 76Graph Qs · 4Assertion–Reason · 3

The big idea, in plain words

A first order reaction is a reaction where the speed depends on how much reactant is left — and on nothing else. Twice as much stuff left means twice the speed. Half as much left means half the speed. That single sentence is the whole chapter unit; everything below is just that sentence written in maths.

Story track

Imagine a room full of popcorn kernels on a hot pan. Every second, each kernel has the same chance of popping. It does not matter whether the kernel is at the edge or the middle, whether it is early in the cooking or late. Every unpopped kernel, every second, has the same small chance.

At the start there are 1000 kernels, so lots of pops per second — it sounds loud. Later only 100 kernels are left, so you hear about a tenth as many pops per second. The kernels did not get lazy. Each one still has exactly the same chance. There are simply fewer of them left to pop.

That is a first order reaction. The rate falls not because the molecules slow down, but because there are fewer molecules left to react.

Now here is the strange and beautiful part. Ask: how long until half the kernels have popped? Say it takes 30 seconds to go from 1000 to 500. How long from 500 to 250? Also 30 seconds. From 250 to 125? Again 30 seconds. The time to halve is always the same, no matter how much you start with. That fixed time has a name: the half-life, written t½.

This is why first order questions are so easy once you see it. You are not really doing chemistry. You are counting halvings.

Why doesn't the half-life depend on the starting amount? Because doubling the amount doubles the number of molecules that must disappear, but it also doubles the speed at which they disappear. The two doublings cancel exactly. A bigger crowd empties a bigger hall in the same time, provided every person leaves at the same personal rate.

From "rate depends on amount" to a usable equation

Maths track

Take R → P. First order means the rate is proportional to the first power of [R]:

Rate = −d[R]/dt = k[R]

Separate the variables — put everything with [R] on one side and everything with t on the other:

d[R]/[R] = −k dt

Integrate both sides. The left side integrates to ln[R], the right to −kt plus a constant:

ln[R] = −kt + I

Find I using the starting condition. At t = 0 the concentration is [R]₀, so ln[R]₀ = I. Put that back:

ln[R] = −kt + ln[R]₀

Rearrange into the three forms you will actually use in the exam:

ln([R]/[R]₀) = −kt [R] = [R]₀·e^(−kt) k = (2.303/t)·log([R]₀/[R])

The last one has the 2.303 because we switched from natural log to base-10 log: ln x = 2.303 log x. Indian exam papers overwhelmingly use the log₁₀ form, so make that your default.

Deriving the half-life — the two-line derivation you should be able to write blind

Maths track

Half-life means the time when [R] has fallen to [R]₀/2. Substitute that into the log form:

k = (2.303/t½)·log([R]₀ / ([R]₀/2)) = (2.303/t½)·log 2

The [R]₀ cancels — this cancellation is the entire reason half-life is independent of starting concentration. With log 2 = 0.301:

t½ = 2.303 × 0.301 / k = 0.693 / k

Note 0.693 is just ln 2. So the cleaner way to remember it is t½ = ln2 / k.

The halving ladder — where most marks are won

Because each half-life removes half of whatever remains, after n half-lives:

[R] = [R]₀ / 2ⁿ fraction remaining = (1/2)ⁿ n = t / t½
nTime elapsedFraction left% completedRecognise it as
11/250%One halving
22t½1/475%Very commonly asked
33t½1/887.5%Commonly asked
44t½1/1693.75%NCERT Q 3.16
55t½1/3296.875%Occasional
1010t½1/1024≈99.9%NCERT Example 3.8
The single most useful reflex in this unit. The instant a question gives you a "nice" fraction — 1/2, 1/4, 1/8, 1/16, 1/32, 1/64 — stop calculating. Count halvings and multiply by t½. Reaching for logs there costs you forty seconds you do not have.

The percentage-completion shortcuts

When the fraction is not a power of ½ you must use logs — but four values come up so often that learning them outright is worth it. Setting t = (2.303/k)·log(100/(100−x)):

Completionk·t equalsIn half-livesWhere it appears
50%0.6931.00Definition of t½
75%1.3862.00Exactly 2 half-lives
90%2.3033.32Very frequent
99%4.6066.64NCERT Q 3.18
99.9%6.9099.97 ≈ 10NCERT Example 3.8
Two ratios that are themselves exam questions. t₉₉ = 2 × t₉₀ (because log100 = 2×log10) and t₉₉.₉ = 3 × t₉₀ = 10 × t½. These are asked as "show that…" in NCERT and as one-liners in NEET.

What makes first order special — the four consequences

Beyond the textbook: why radioactivity lives in this chapter

NCERT tells you that all natural and artificial radioactive decay follows first order kinetics, then moves on. It is worth one extra minute of thought, because NEET dresses kinetics questions in radioactive clothing regularly.

Story track

A radioactive nucleus has no memory and no age. A carbon-14 nucleus that has been sitting in a tree for 4000 years is not "more likely" to decay today than one made yesterday. Each nucleus, each second, has the same fixed chance of falling apart — exactly like the popcorn kernels. Nothing external influences it: heating it, freezing it, dissolving it or squeezing it changes nothing.

So radioactive decay is automatically first order, and every formula on this page applies unchanged. Just read "number of nuclei N" wherever the page says "concentration [R]".

N = N₀·e^(−λt) λ = 0.693/t½ Activity A = λN, so A/A₀ = N/N₀

Carbon dating works because a living tree keeps swapping carbon with the air, holding its ¹⁴C level fixed. The moment it dies the swapping stops and the ¹⁴C clock starts running down. Measure how much is left, count the halvings, get the age.

The one distinction that costs marks. "80% of the ¹⁴C remains" and "80% has decayed" are opposite statements. Read the sentence twice. The NCERT problem (Q 3.14) says the artifact had only 80% of the ¹⁴C found in a living tree — meaning 80% remains, only 20% has gone.

Gap content — worth knowing, not in your NCERT text

Half-life for a general order n: t½ ∝ 1/[R]₀(n−1). Check it: for n = 1 the power is zero, so t½ is independent of [R]₀ — matches. For n = 0 the power is −1, so t½ ∝ [R]₀ — also matches. Questions of the form "t½ becomes double when initial concentration is halved, find the order" are solved only by this relation, and they do appear.
Average life (mean life): τ = 1/k = t½/0.693 = 1.44 t½. Occasionally asked in radioactivity-flavoured questions; not derived in NCERT.

See it move — four animations

Each one isolates a single idea. Work through them in order; the fourth is the one that stops the zero-order/first-order half-life confusion for good.

ANIM 1
The halving ladder — watch 256 molecules disappear
Half-lives elapsed: 0 Molecules left: 256 / 256
Time elapsed: 0 × t½
Fraction remaining: 1/1 = 100%
Reaction completed: 0%

Press the step button and one half-life passes. Green dots are unreacted molecules, grey are reacted. Notice that the number removed shrinks each step (128, then 64, then 32…) but the fraction removed is always exactly one half. That is the definition of first order, shown rather than stated.

ANIM 2
Why the log plot straightens the curve
[R] t ln[R] t Curved — exponential decay Straight — slope = −k

The left panel is what nature does — a curve that flattens out and never quite touches zero. The right panel is the same data with ln[R] on the vertical axis, and it is dead straight with slope −k. This is the whole reason chemists plot logs: a straight line is easy to read a rate constant off, a curve is not. Slide k and watch both panels respond together. The green dashed steps on the left mark successive half-lives — they are evenly spaced, always.

ANIM 3
The completion ruler — reading time in half-lives
0 10 × t½ Completion reached 50.00%

Drag the slider to move along a timeline measured in half-lives. The brass ticks mark the percentages NEET asks about. Two things to absorb: 75% sits exactly on 2 half-lives (a clean number worth memorising), while 90% sits at 3.32 — not 3 — which is exactly why 90% questions need logs and 75% questions do not.

ANIM 4
Zero order vs first order — which half-life moves?
[R] t [R] t ZERO ORDER FIRST ORDER

Slide the starting concentration. On the zero-order side the half-life marker slides with it, because t½ = [R]₀/2k is proportional to where you started. On the first-order side the marker does not budge, no matter how high or low you start. If you understand this one picture, you will never confuse the two half-life formulas again.

Formula sheet

Everything you need for this unit. The five bolded working forms — log form, half-life, halving ladder, percentage completion and the standard kt values — cover well over ninety percent of questions.

Quantity / situationFormulaWhen you use it
Differential rate lawRate = −d[R]/dt = k[R]Definition of first order; starting point for the derivation
Integrated law (ln form)ln[R] = ln[R]₀ − ktStraight-line form; use when a graph is involved
Integrated law (exponential)[R] = [R]₀·e^(−kt)When asked for concentration left after a given time
Integrated law (log₁₀ form)k = (2.303/t)·log([R]₀/[R])The default working form for NEET numericals
Two-time formk = 2.303/(t₂−t₁) · log([R]₁/[R]₂)When neither reading is the initial concentration
Half-lifet½ = 0.693/k = ln2/kThe most-used single line in the chapter
After n half-lives[R] = [R]₀/2ⁿ ; n = t/t½Whenever the fraction is 1/2, 1/4, 1/8, 1/16…
Fraction remaining at time t[R]/[R]₀ = e^(−kt) = (1/2)^(t/t½)Either form works; pick whichever the data suits
Time for x% completiont = (2.303/k)·log(100/(100−x))For 90%, 99%, 99.9% and other non-power-of-2 values
Standard completion timeskt₅₀=0.693, kt₇₅=1.386, kt₉₀=2.303, kt₉₉=4.606, kt₉₉.₉=6.909Memorise; converts most questions to one division
Useful ratiost₉₉ = 2t₉₀ ; t₉₉.₉ = 3t₉₀ = 10t½ ; t₇₅ = 2t½Asked directly as 'show that' or as one-liners
Units of ktime⁻¹ (s⁻¹, min⁻¹, h⁻¹, yr⁻¹)Seeing these units identifies first order instantly
Graph: ln[R] vs tslope = −k, intercept = ln[R]₀Straight, falling
Graph: log([R]₀/[R]) vs tslope = k/2.303, passes through originStraight, rising
Graph: t½ vs [R]₀horizontal lineThe signature test for first order
Radioactive decayN = N₀e^(−λt) ; λ = 0.693/t½ ; A/A₀ = N/N₀Same maths, different symbols
Mean (average) life — gap contentτ = 1/k = 1.44 t½Not in NCERT; appears in decay-flavoured questions
General-order half-life — gap contentt½ ∝ 1/[R]₀^(n−1)For 'find the order from how t½ changes' questions

76 NEET-type questions with worked solutions

Four graph questions and three assertion–reason questions are included, marked with coloured left borders. Questions tagged PYQ pattern follow forms that have appeared in NEET/AIPMT papers or are lifted from NCERT exercises — exact year attributions are deliberately omitted rather than guessed. Attempt each question first, then open the solution and check not only your answer but your route: in this unit the fast route and the slow route give the same mark but not the same time.

Q01PYQ pattern

A first order reaction has a rate constant k = 5.5 × 10⁻¹⁴ s⁻¹. Its half-life is:

Given

k = 5.5 × 10⁻¹⁴ s⁻¹, first order

Asked

Concept

For first order the half-life is fixed by k alone.

Formula

t½ = 0.693/k

Baby steps
  1. Write t½ = 0.693 / (5.5 × 10⁻¹⁴).
  2. Divide the numbers: 0.693 / 5.5 = 0.126.
  3. Handle the power: dividing by 10⁻¹⁴ means multiplying by 10¹⁴, so 0.126 × 10¹⁴.
  4. Standardise: 0.126 × 10¹⁴ = 1.26 × 10¹³ s.

Answer · (a) 1.26 × 10¹³ s

Shortcut · k in the 10⁻ⁿ range always throws t½ into the 10⁺ⁿ range. Get 0.693/5.5 = 0.126 first, then fix the exponent.
Q02PYQ pattern

The time required to decompose SO₂Cl₂ to half of its initial amount is 60 minutes. If the decomposition is first order, the rate constant is:

Given

t½ = 60 min, first order

Asked

k in s⁻¹

Concept

Rearrange the half-life relation; then convert the time unit.

Formula

k = 0.693/t½

Baby steps
  1. In minutes: k = 0.693/60 = 0.01155 min⁻¹.
  2. The options are in s⁻¹, so convert. One minute = 60 s, so per-minute must be divided by 60 to become per-second.
  3. k = 0.01155/60 = 1.925 × 10⁻⁴ s⁻¹.

Answer · (a) 1.925 × 10⁻⁴ s⁻¹

Shortcut · Straight to seconds: t½ = 3600 s, so k = 0.693/3600 = 1.925 × 10⁻⁴ s⁻¹.
Q03

For a first order reaction the half-life is 6.93 minutes. The rate constant, in min⁻¹, is:

Given

t½ = 6.93 min

Asked

k

Concept

Direct substitution.

Formula

k = 0.693/t½

Baby steps
  1. k = 0.693 / 6.93.
  2. Notice 6.93 = 10 × 0.693, so the ratio is exactly 1/10.
  3. k = 0.1 min⁻¹.

Answer · (a) 0.1 min⁻¹

Shortcut · When t½ is a tidy multiple of 0.693, cancel rather than divide.
Q04

The half-life of a first order reaction is 20 minutes. The rate constant, expressed in s⁻¹, is closest to:

Given

t½ = 20 min = 1200 s

Asked

k in s⁻¹

Concept

Convert to seconds before dividing, so no second conversion is needed.

Formula

k = 0.693/t½

Baby steps
  1. t½ in seconds = 20 × 60 = 1200 s.
  2. k = 0.693/1200.
  3. 0.693/1200 = 5.775 × 10⁻⁴ ≈ 5.8 × 10⁻⁴ s⁻¹.

Answer · (a) 5.8 × 10⁻⁴ s⁻¹

Q05PYQ pattern

A first order reaction is 50% complete in 30 minutes. The time taken for it to be 50% complete when the initial concentration is doubled will be:

Given

First order, t½ = 30 min at some [R]₀; then [R]₀ is doubled

Asked

new t½

Concept

The defining property of first order: half-life is independent of initial concentration.

Formula

t½ = 0.693/k — no [R]₀ term appears

Baby steps
  1. Write t½ = 0.693/k and look for [R]₀ in it.
  2. There is none. k depends only on temperature, not on how much you started with.
  3. So doubling [R]₀ leaves the half-life untouched: still 30 minutes.

Answer · (a) 30 minutes

Shortcut · Any first order question that changes [R]₀ and asks about t½ has the answer 'unchanged'.
Q06

If the rate constant of a first order reaction is 2.31 × 10⁻³ s⁻¹, the half-life in minutes is about:

Given

k = 2.31 × 10⁻³ s⁻¹

Asked

t½ in minutes

Concept

Compute in seconds, then convert.

Formula

t½ = 0.693/k

Baby steps
  1. t½ = 0.693 / 2.31 × 10⁻³.
  2. 0.693/2.31 = 0.30, so t½ = 0.30 × 10³ = 300 s.
  3. 300 s ÷ 60 = 5 minutes.

Answer · (a) 5 minutes

Q07

For a first order reaction, if k = 0.0693 min⁻¹, the time in which the reaction is 50% complete is:

Given

k = 0.0693 min⁻¹

Asked

time for 50% completion

Concept

50% completion IS the half-life — no separate calculation needed.

Formula

t½ = 0.693/k

Baby steps
  1. Recognise that 50% complete means half the reactant is gone, which is the definition of t½.
  2. t½ = 0.693/0.0693 = 10 minutes.

Answer · (a) 10 min

Shortcut · Never set up a log calculation for 50%. Read it as t½ immediately.
Q08

The rate constant of a first order reaction is 3 × 10⁻⁴ s⁻¹. The reaction is carried out at a higher temperature where k doubles. The half-life then:

Given

k doubles

Asked

effect on t½

Concept

t½ and k are inversely proportional.

Formula

t½ = 0.693/k

Baby steps
  1. t½ ∝ 1/k.
  2. If k is multiplied by 2, then t½ is multiplied by 1/2.
  3. The half-life is halved.

Answer · (a) becomes half

Q09PYQ pattern

The rate constant for a first order reaction is 60 s⁻¹. The time taken to reduce the initial concentration of the reactant to its 1/16th value is:

Given

k = 60 s⁻¹; final concentration = [R]₀/16

Asked

t

Concept

1/16 is a power of one half, so count halvings rather than using logs.

Formula

[R] = [R]₀/2ⁿ ; t = n·t½ ; t½ = 0.693/k

Baby steps
  1. Write 1/16 as (1/2)⁴, so n = 4 half-lives.
  2. t½ = 0.693/60 = 0.01155 s.
  3. t = 4 × 0.01155 = 0.0462 s = 4.62 × 10⁻² s.

Answer · (a) 4.62 × 10⁻² s

Shortcut · 1/2→1, 1/4→2, 1/8→3, 1/16→4 half-lives. Multiply and you are done.
Q10

A first order reaction has a half-life of 10 minutes. What fraction of the reactant remains after 40 minutes?

Given

t½ = 10 min, t = 40 min

Asked

fraction remaining

Concept

Count how many half-lives fit into the elapsed time.

Formula

n = t/t½ ; fraction = (1/2)ⁿ

Baby steps
  1. n = 40/10 = 4 half-lives.
  2. Fraction remaining = (1/2)⁴ = 1/16.

Answer · (a) 1/16

Q11

1 g of a radioactive substance with half-life 5 years is stored. The mass remaining after 20 years is:

Given

N₀ = 1 g, t½ = 5 yr, t = 20 yr

Asked

mass remaining

Concept

Radioactive decay is first order; the halving ladder applies unchanged.

Formula

N = N₀/2ⁿ, n = t/t½

Baby steps
  1. n = 20/5 = 4 half-lives.
  2. N = 1/2⁴ = 1/16 g.
  3. 1/16 = 0.0625 g.

Answer · (a) 0.0625 g

Q12PYQ pattern

A first order reaction is 75% complete in 60 minutes. Its half-life is:

Given

75% complete in 60 min

Asked

Concept

75% complete means 25% (= 1/4) remains, and 1/4 is exactly two half-lives.

Formula

t₇₅ = 2 t½

Baby steps
  1. 75% gone leaves 25% = 1/4 of the original.
  2. 1/4 = (1/2)², so exactly 2 half-lives have passed.
  3. 2 t½ = 60 min, so t½ = 30 min.

Answer · (a) 30 min

Shortcut · 75% ↔ 2 half-lives is worth memorising outright; it appears constantly.
Q13

A sample decays to 1/8th of its original amount in 30 minutes by first order kinetics. The rate constant is:

Given

Fraction left = 1/8 after 30 min

Asked

k

Concept

Convert the fraction to half-lives, get t½, then get k.

Formula

1/8 = (1/2)³ ; t½ = t/3 ; k = 0.693/t½

Baby steps
  1. 1/8 = (1/2)³, so n = 3 half-lives.
  2. 3 t½ = 30 min, giving t½ = 10 min.
  3. k = 0.693/10 = 0.0693 min⁻¹.

Answer · (a) 0.0693 min⁻¹

Q14

For a first order reaction, 87.5% of the reactant is consumed in 45 minutes. The rate constant is nearest to:

Given

87.5% consumed in 45 min

Asked

k

Concept

87.5% gone leaves 12.5% = 1/8, which is three half-lives.

Formula

t½ = t/3 ; k = 0.693/t½

Baby steps
  1. Remaining = 100 − 87.5 = 12.5% = 1/8.
  2. 1/8 = (1/2)³, so n = 3 and t½ = 45/3 = 15 min.
  3. k = 0.693/15 = 0.0462 min⁻¹.

Answer · (a) 0.0462 min⁻¹

Q15PYQ pattern

Consider A → products with k = 2.0 × 10⁻² s⁻¹. If [A]₀ = 1.0 mol L⁻¹, the concentration of A remaining after 100 s is:

Given

k = 2.0 × 10⁻² s⁻¹, [A]₀ = 1.0 M, t = 100 s

Asked

[A] at 100 s

Concept

The exponential form is fastest when time and k are both given.

Formula

[A] = [A]₀ e^(−kt)

Baby steps
  1. Compute the exponent: kt = 2.0 × 10⁻² × 100 = 2.
  2. [A] = 1.0 × e⁻² .
  3. e⁻² = 0.1353, so [A] ≈ 0.135 mol L⁻¹.

Answer · (a) 0.135 mol L⁻¹

Shortcut · Learn e⁻¹ = 0.368, e⁻² = 0.135, e⁻³ = 0.050. NEET reuses these three constantly.
Q16PYQ pattern

Sucrose decomposes in acid solution into glucose and fructose by first order kinetics with t½ = 3.00 hours. The fraction of sucrose remaining after 8 hours is about:

Given

t½ = 3.00 h, t = 8 h

Asked

fraction remaining

Concept

Non-integer number of half-lives — use the power form directly.

Formula

fraction = (1/2)^(t/t½)

Baby steps
  1. n = 8/3 = 2.667 half-lives.
  2. Fraction = (0.5)^2.667.
  3. Alternatively: k = 0.693/3 = 0.231 h⁻¹, so kt = 0.231 × 8 = 1.848, and fraction = e^(−1.848).
  4. Either route gives 0.158, i.e. about 15.8% remains.

Answer · (a) 0.158

Shortcut · Bracket it first: 8 h is between 2 and 3 half-lives, so the answer must lie between 0.25 and 0.125. Only one option does.
Q17

After 3 half-lives, the percentage of a first order reactant that has reacted is:

Given

n = 3 half-lives

Asked

percentage reacted

Concept

Distinguish 'remaining' from 'reacted' — the question asks for reacted.

Formula

remaining = (1/2)ⁿ ; reacted = 1 − (1/2)ⁿ

Baby steps
  1. Remaining = (1/2)³ = 1/8 = 12.5%.
  2. Reacted = 100 − 12.5 = 87.5%.

Answer · (a) 87.5%

Shortcut · The trap option is 12.5%, the amount left. Underline whether the question says 'left' or 'reacted' before you choose.
Q18PYQ pattern

A first order reaction has a rate constant 1.15 × 10⁻³ s⁻¹. How long will 5 g of the reactant take to reduce to 3 g?

Given

k = 1.15 × 10⁻³ s⁻¹, [R]₀ = 5 g, [R] = 3 g

Asked

t

Concept

Mass may be used in place of concentration because only their ratio matters.

Formula

t = (2.303/k)·log([R]₀/[R])

Baby steps
  1. Ratio [R]₀/[R] = 5/3 = 1.667.
  2. log 1.667 = 0.2218.
  3. 2.303/k = 2.303/(1.15 × 10⁻³) = 2003.
  4. t = 2003 × 0.2218 = 444 s.

Answer · (a) 444 s

Shortcut · Grams, moles, pressures, counts — any consistent measure works, since the units cancel in the ratio.
Q19PYQ pattern

A first order reaction takes 40 minutes for 30% decomposition. Its t½ is nearest to:

Given

30% decomposed in 40 min

Asked

Concept

Find k from the log form first, then convert to half-life.

Formula

k = (2.303/t)·log(100/(100−x)) ; t½ = 0.693/k

Baby steps
  1. 30% decomposed leaves 70%, so [R]₀/[R] = 100/70 = 1.4286.
  2. log 1.4286 = 0.1549.
  3. k = (2.303/40) × 0.1549 = 0.05758 × 0.1549 = 8.918 × 10⁻³ min⁻¹.
  4. t½ = 0.693 / 8.918 × 10⁻³ = 77.7 min.

Answer · (a) 77.7 min

Shortcut · Sanity check: only 30% is gone in 40 min, so half-life must be comfortably more than 40 min. That alone eliminates (b) and (d).
Q20

For a first order reaction, the time required for 90% completion is:

Given

90% completion, first order

Asked

t in terms of k

Concept

Substitute x = 90 into the completion formula and simplify.

Formula

t = (2.303/k)·log(100/(100−x))

Baby steps
  1. Remaining = 10%, so the ratio is 100/10 = 10.
  2. log 10 = 1 exactly.
  3. t = (2.303/k) × 1 = 2.303/k.

Answer · (a) 2.303/k

Shortcut · 90% is the friendliest case because log 10 = 1. Similarly 99% gives log 100 = 2, so t = 4.606/k.
Q21PYQ pattern

Show-that type: for a first order reaction, the time required for 99% completion compared with that for 90% completion is:

Given

First order

Asked

ratio t₉₉ : t₉₀

Concept

Both reduce to logs of powers of ten, so the ratio is clean.

Formula

t = (2.303/k)·log([R]₀/[R])

Baby steps
  1. t₉₀: remaining 10%, ratio 10, log 10 = 1, so t₉₀ = 2.303/k.
  2. t₉₉: remaining 1%, ratio 100, log 100 = 2, so t₉₉ = 4.606/k.
  3. Divide: t₉₉ / t₉₀ = 4.606/2.303 = 2.

Answer · (a) twice

Shortcut · Ratios of completion times are ratios of logs. 99:90 gives 2:1, and 99.9:90 gives 3:1.
Q22PYQ pattern

For a first order reaction, the time required for 99.9% completion is how many times the half-life?

Given

99.9% completion

Asked

t₉₉.₉ / t½

Concept

Compare two expressions in k; k cancels.

Formula

t = (2.303/k)·log([R]₀/[R]) ; t½ = 0.693/k

Baby steps
  1. Remaining = 0.1%, so ratio = 1000 and log 1000 = 3.
  2. t₉₉.₉ = 3 × 2.303/k = 6.909/k.
  3. Divide by t½ = 0.693/k: the k cancels, leaving 6.909/0.693 = 9.97 ≈ 10.

Answer · (a) about 10 times

Shortcut · This is NCERT Example 3.8 verbatim — expect it in some form.
Q23

A first order reaction is 20% complete in 10 minutes. The time taken for it to be 60% complete is nearest to:

Given

20% complete in 10 min

Asked

time for 60% completion

Concept

Get k from the first piece of data, then use it for the second.

Formula

k = (2.303/t)·log(100/(100−x))

Baby steps
  1. Step 1 — find k: remaining 80%, ratio 100/80 = 1.25, log 1.25 = 0.0969.
  2. k = (2.303/10) × 0.0969 = 0.02231 min⁻¹.
  3. Step 2 — use k for 60%: remaining 40%, ratio 100/40 = 2.5, log 2.5 = 0.3979.
  4. t = (2.303/0.02231) × 0.3979 = 103.2 × 0.3979 = 41.1 min.

Answer · (a) about 41 min

Shortcut · Two-stage questions always follow the same shape: data → k → answer. Never try to jump straight across.
Q24

If a first order reaction is 10% complete in 20 minutes, the time for 19% completion is approximately:

Given

10% complete in 20 min

Asked

time for 19% completion

Concept

Remaining fractions multiply. 0.90 × 0.90 = 0.81, so 19% completion is exactly two intervals.

Formula

fraction remaining after two equal intervals = (0.9)² = 0.81

Baby steps
  1. After 20 min, 90% remains.
  2. After another 20 min, 90% of that 90% remains = 81%.
  3. 81% remaining means 19% complete, at t = 40 min.

Answer · (a) 40 min

Shortcut · First order fractions are multiplicative. Spotting 0.81 = 0.9² saves the entire log calculation.
Q25

The concentration of a reactant falls from 0.8 M to 0.2 M in 20 minutes by first order kinetics. The rate constant is:

Given

[R]₀ = 0.8 M, [R] = 0.2 M, t = 20 min

Asked

k

Concept

0.8 → 0.2 is a factor of 4, which is two half-lives.

Formula

1/4 = (1/2)² ; t½ = t/2 ; k = 0.693/t½

Baby steps
  1. 0.2/0.8 = 1/4, so n = 2 half-lives.
  2. t½ = 20/2 = 10 min.
  3. k = 0.693/10 = 0.0693 min⁻¹.

Answer · (a) 0.0693 min⁻¹

Q26

For a first order reaction, if 0.6 of the reactant remains after time t, then kt equals:

Given

Fraction remaining = 0.6

Asked

kt

Concept

kt is just the natural log of the inverse fraction.

Formula

kt = ln([R]₀/[R]) = 2.303·log([R]₀/[R])

Baby steps
  1. [R]₀/[R] = 1/0.6 = 1.667.
  2. log 1.667 = 0.2218.
  3. kt = 2.303 × 0.2218 = 0.511.

Answer · (a) 0.511

Q27

A first order reaction requires 100 minutes for 50% completion. The time required for 90% completion under identical conditions is nearest to:

Given

t½ = 100 min

Asked

t₉₀

Concept

90% completion always corresponds to 3.32 half-lives.

Formula

t₉₀ = 2.303/k and t½ = 0.693/k, so t₉₀ = 3.32 t½

Baby steps
  1. Take the ratio: t₉₀/t½ = 2.303/0.693 = 3.32.
  2. t₉₀ = 3.32 × 100 = 332 min.

Answer · (a) 332 min

Shortcut · Memorise the multipliers of t½: 75% → 2, 90% → 3.32, 99% → 6.64, 99.9% → 10.
Q28PYQ pattern

The half-life for radioactive decay of ¹⁴C is 5730 years. An archaeological artifact containing wood had only 80% of the ¹⁴C found in a living tree. The age of the sample is about:

Given

t½ = 5730 yr, N/N₀ = 0.80

Asked

age t

Concept

Radioactive decay is first order; find λ from t½ then use the log form.

Formula

λ = 0.693/t½ ; t = (2.303/λ)·log(N₀/N)

Baby steps
  1. λ = 0.693/5730 = 1.2096 × 10⁻⁴ yr⁻¹.
  2. N₀/N = 100/80 = 1.25, and log 1.25 = 0.0969.
  3. 2.303/λ = 2.303 / 1.2096 × 10⁻⁴ = 19039.
  4. t = 19039 × 0.0969 = 1845 years.

Answer · (a) about 1845 years

Shortcut · Sanity check: only 20% has decayed, far less than one half-life, so the age must be well under 5730 years.
Q29PYQ pattern

During nuclear explosion, ⁹⁰Sr with half-life 28.1 years is produced. If 1 μg of ⁹⁰Sr was absorbed in the bones of a newborn, the amount remaining after 10 years (if not lost metabolically) is:

Given

N₀ = 1 μg, t½ = 28.1 yr, t = 10 yr

Asked

N

Concept

Exponential decay with a non-integer number of half-lives.

Formula

N = N₀ e^(−λt), λ = 0.693/t½

Baby steps
  1. λ = 0.693/28.1 = 0.02466 yr⁻¹.
  2. λt = 0.02466 × 10 = 0.2466.
  3. N = 1 × e^(−0.2466) = 0.781 μg.

Answer · (a) 0.781 μg

Shortcut · 10 years is roughly a third of a half-life, so expect somewhat more than 79% left — option (a) is the only plausible one.
Q30PYQ pattern

Continuing the previous data: the amount of ⁹⁰Sr remaining after 60 years is:

Given

N₀ = 1 μg, t½ = 28.1 yr, t = 60 yr

Asked

N

Concept

Same exponential relation with a larger exponent.

Formula

N = N₀ e^(−λt)

Baby steps
  1. λ = 0.693/28.1 = 0.02466 yr⁻¹.
  2. λt = 0.02466 × 60 = 1.4797.
  3. N = e^(−1.4797) = 0.228 μg.

Answer · (a) 0.228 μg

Shortcut · 60 years is just over 2 half-lives, so the answer must sit a little below 0.25 μg.
Q31

A radioactive isotope has a half-life of 20 days. What fraction of the original activity remains after 60 days?

Given

t½ = 20 d, t = 60 d

Asked

fraction of activity remaining

Concept

Activity is proportional to the number of nuclei, so the same halving ladder applies.

Formula

A/A₀ = N/N₀ = (1/2)ⁿ

Baby steps
  1. n = 60/20 = 3 half-lives.
  2. A/A₀ = (1/2)³ = 1/8.

Answer · (a) 1/8

Shortcut · Trap option (d) 1/3 comes from dividing 60 by 20 and inverting — a very common slip.
Q32

The activity of a radioactive sample falls to 1/32 of its original value in 25 minutes. Its half-life is:

Given

A/A₀ = 1/32 in 25 min

Asked

Concept

Read the exponent off the power of two.

Formula

1/32 = (1/2)⁵

Baby steps
  1. 1/32 = (1/2)⁵, so n = 5 half-lives.
  2. 5 t½ = 25 min, giving t½ = 5 min.

Answer · (a) 5 min

Q33

A radioactive nucleus decays with rate constant λ. The mean (average) life of the nucleus is:

Given

Decay constant λ

Asked

mean life τ

Concept

Gap content — mean life is the reciprocal of the decay constant, longer than the half-life.

Formula

τ = 1/λ = t½/0.693 = 1.44 t½

Baby steps
  1. Mean life is defined as the reciprocal of the rate constant: τ = 1/λ.
  2. Relate it to half-life: since λ = 0.693/t½, τ = t½/0.693 = 1.44 t½.
  3. So the mean life is always longer than the half-life.

Answer · (a) 1/λ

Shortcut · Remember the order: τ > t½ always, by a factor of 1.44.
Q34

Two radioactive samples X and Y have half-lives of 10 and 20 minutes respectively. If they start with equal numbers of nuclei, after 20 minutes the ratio N(X) : N(Y) will be:

Given

t½(X) = 10 min, t½(Y) = 20 min, equal N₀, t = 20 min

Asked

N(X):N(Y)

Concept

Count half-lives separately for each sample.

Formula

N = N₀(1/2)^(t/t½)

Baby steps
  1. For X: n = 20/10 = 2, so N(X) = N₀/4.
  2. For Y: n = 20/20 = 1, so N(Y) = N₀/2.
  3. Ratio = (N₀/4) : (N₀/2) = 1 : 2.

Answer · (a) 1 : 2

Shortcut · Shorter half-life always means less remaining. That eliminates any option putting X above Y.
Q35Graph

For a first order reaction, which plot gives a straight line with slope equal to −k?

ln[R]tslope = ?
Given

First order reaction, straight line of slope −k required

Asked

Which variables to plot

Concept

Put the integrated law into y = mx + c form and read off which quantity is y.

Formula

ln[R] = −kt + ln[R]₀

Baby steps
  1. Compare ln[R] = −kt + ln[R]₀ with y = mx + c.
  2. y is ln[R], x is t, the slope m is −k and the intercept c is ln[R]₀.
  3. So plotting ln[R] against t gives a falling straight line of slope −k.
  4. Check the others: [R] vs t is a curve for first order; log([R]₀/[R]) vs t is straight but rises with slope +k/2.303; 1/[R] vs t belongs to second order.

Answer · (a) ln[R] versus t

Shortcut · Slope −k means the plotted quantity must fall. Only ln[R] vs t falls with that exact slope.
Q36Graph

The graph shown plots half-life against initial concentration for a certain reaction. The order of the reaction is:

[R]₀
Given

t½ versus [R]₀ is a horizontal line

Asked

order of reaction

Concept

A horizontal line means the half-life does not change with initial concentration — the signature of first order.

Formula

t½ ∝ 1/[R]₀^(n−1)

Baby steps
  1. Horizontal means t½ is constant as [R]₀ varies.
  2. In t½ ∝ 1/[R]₀^(n−1), independence requires the exponent (n−1) to be zero.
  3. n − 1 = 0 gives n = 1, so the reaction is first order.
  4. Cross-check: zero order would give a rising straight line through the origin, and second order a falling hyperbola.

Answer · (a) first order

Shortcut · Flat line → first order. Rising line → zero order. Falling curve → second order.
Q37Graph

The plot of log([R]₀/[R]) against time for a first order reaction gives a straight line through the origin. Its slope equals:

log([R]₀/[R])t
Given

Straight line of log([R]₀/[R]) versus t through the origin

Asked

slope

Concept

Rearrange the base-10 integrated form into y = mx.

Formula

k = (2.303/t)·log([R]₀/[R])

Baby steps
  1. Rearrange for the plotted quantity: log([R]₀/[R]) = (k/2.303)·t.
  2. Compare with y = mx: the slope is k/2.303 and the intercept is zero, so the line passes through the origin.
  3. The slope is positive because [R]₀/[R] grows as the reaction proceeds.

Answer · (a) k/2.303

Shortcut · If the line rises, the slope carries a plus sign; the 2.303 always sits underneath k in the log₁₀ version.
Q38Graph

Two first order reactions A and B are plotted as ln[R] against t on the same axes. Line A is steeper than line B. Which statement is correct?

ABln[R]t
Given

Both first order; |slope of A| > |slope of B|

Asked

Comparison of k and t½

Concept

Slope magnitude is k; half-life is inversely proportional to k.

Formula

slope = −k ; t½ = 0.693/k

Baby steps
  1. The magnitude of the slope equals k, so a steeper line means a larger k.
  2. A is steeper, therefore k(A) > k(B).
  3. Since t½ = 0.693/k, a larger k gives a shorter half-life.
  4. So A has both the larger rate constant and the shorter half-life.

Answer · (a) A has the larger k and the shorter half-life

Shortcut · Steeper = faster = larger k = shorter half-life. The three go together, always.
Q39Assertion–Reason

Assertion (A): The half-life of a first order reaction does not depend on the initial concentration of the reactant.
Reason (R): In the derivation of t½ for a first order reaction, the initial concentration term cancels out.

Given

Statements about first order half-life

Asked

Truth values and whether R explains A

Concept

Test each statement independently, then ask whether R is the actual cause of A.

Formula

k = (2.303/t½)·log([R]₀ / ([R]₀/2))

Baby steps
  1. Check A: t½ = 0.693/k contains no concentration term, so A is true.
  2. Check R: in the derivation, [R]₀/([R]₀/2) simplifies to 2, so the initial concentration genuinely cancels. R is true.
  3. Does R explain A? Yes — the cancellation is precisely why no concentration term survives into the final formula.
  4. So both are true and R is the correct explanation.

Answer · (a) Both A and R are true and R is the correct explanation of A

Q40Assertion–Reason

Assertion (A): A first order reaction can never be 100% complete in finite time.
Reason (R): The concentration in a first order reaction decays exponentially and approaches zero only asymptotically.

Given

Statements about completion of a first order reaction

Asked

Truth values and explanation

Concept

An exponential function never reaches zero for any finite argument.

Formula

[R] = [R]₀ e^(−kt) ; t = (2.303/k)·log([R]₀/[R])

Baby steps
  1. Check A: setting [R] = 0 in t = (2.303/k)·log([R]₀/[R]) requires log of infinity, so t would be infinite. A is true.
  2. Check R: e^(−kt) shrinks towards zero but is positive for every finite t, so the approach is asymptotic. R is true.
  3. R gives exactly the mathematical reason for A, so it is the correct explanation.
  4. This is why exam questions ask for 99% or 99.9% completion but never 100%.

Answer · (a) Both A and R are true and R is the correct explanation of A

Q41Assertion–Reason

Assertion (A): For a first order reaction, doubling the initial concentration doubles the rate but leaves the rate constant unchanged.
Reason (R): The rate constant depends on temperature but not on the concentration of the reactants.

Given

Statements distinguishing rate from rate constant

Asked

Truth values and explanation

Concept

Rate and rate constant are different quantities — the first depends on concentration, the second does not.

Formula

Rate = k[R] ; k = A e^(−Ea/RT)

Baby steps
  1. Check A: since Rate = k[R], doubling [R] doubles the rate. And k itself has no concentration term, so it is unchanged. A is true.
  2. Check R: the Arrhenius expression k = A e^(−Ea/RT) contains temperature but no concentration. R is true.
  3. R states exactly why k stays fixed while the rate changes, so it explains A.
  4. The distinction between 'rate' and 'rate constant' is one of the most frequently tested ideas in this chapter.

Answer · (a) Both A and R are true and R is the correct explanation of A

Q42PYQ pattern

Which of the following units unambiguously indicates a first order reaction?

Given

Units of the rate constant

Asked

Which corresponds to first order

Concept

The general unit of k is (mol L⁻¹)^(1−n) time⁻¹; for n = 1 the concentration term vanishes.

Formula

units of k = (mol L⁻¹)^(1−n)·time⁻¹

Baby steps
  1. Put n = 1: the exponent (1 − n) becomes zero, so the concentration factor is (mol L⁻¹)⁰ = 1.
  2. That leaves only time⁻¹, i.e. s⁻¹.
  3. Check the others: mol L⁻¹ s⁻¹ is zero order, L mol⁻¹ s⁻¹ is second order, mol⁻² L² s⁻¹ is third order.

Answer · (a) s⁻¹

Shortcut · No concentration in the units → first order. This is the fastest single mark in the chapter.
Q43

For a first order reaction A → B, which of the following remains constant as the reaction proceeds?

Given

A first order reaction proceeding with time

Asked

The constant quantity

Concept

Only k is fixed at a given temperature; everything else changes.

Formula

Rate = k[A]

Baby steps
  1. [A] falls with time and [B] rises, so both concentrations change.
  2. Since Rate = k[A] and [A] is falling, the rate falls too.
  3. k depends only on temperature and activation energy, so at fixed temperature it stays constant.

Answer · (a) The rate constant k

Q44

The hydrogenation of ethene, C₂H₄(g) + H₂(g) → C₂H₆(g), has rate = k[C₂H₄]. This means the reaction is:

Given

Rate = k[C₂H₄]

Asked

overall order

Concept

Overall order is the sum of the exponents in the experimental rate law.

Formula

order = sum of exponents in Rate = k[A]ˣ[B]ʸ

Baby steps
  1. The exponent of [C₂H₄] is 1.
  2. [H₂] does not appear at all, so its exponent is 0.
  3. Overall order = 1 + 0 = 1, i.e. first order.

Answer · (a) first order overall

Shortcut · A reactant missing from the rate law contributes zero, not one. Do not add a phantom exponent.
Q45

For a first order reaction, the plot of rate against concentration of the reactant is:

Given

Rate = k[R], first order

Asked

Shape of rate versus concentration

Concept

Rate is directly proportional to concentration, which is the equation of a line through the origin.

Formula

Rate = k[R]

Baby steps
  1. Compare Rate = k[R] with y = mx: y is the rate, x is the concentration, and the slope is k.
  2. There is no constant term, so the line passes through the origin.
  3. Zero order would instead give a horizontal line, and second order a parabola.

Answer · (a) a straight line through the origin

Q46PYQ pattern

The decomposition of N₂O₅ at 318 K is first order with initial concentration 1.24 × 10⁻² mol L⁻¹, falling to 0.20 × 10⁻² mol L⁻¹ in 60 minutes. The rate constant is:

Given

[R]₁ = 1.24 × 10⁻² M, [R]₂ = 0.20 × 10⁻² M, t = 60 min

Asked

k

Concept

Standard two-concentration log calculation.

Formula

k = (2.303/t)·log([R]₁/[R]₂)

Baby steps
  1. Ratio = 1.24 × 10⁻² / 0.20 × 10⁻² = 6.2 (the powers of ten cancel).
  2. log 6.2 = 0.7924.
  3. k = (2.303/60) × 0.7924 = 0.03838 × 0.7924.
  4. k = 0.0304 min⁻¹.

Answer · (a) 0.0304 min⁻¹

Shortcut · Cancel matching powers of ten before touching the log table — it removes the commonest arithmetic slip here.
Q47

A first order reaction has k = 0.1155 min⁻¹. The fraction of reactant left after 12 minutes is nearest to:

Given

k = 0.1155 min⁻¹, t = 12 min

Asked

fraction remaining

Concept

Convert k to a half-life and count halvings — faster than exponentials.

Formula

t½ = 0.693/k ; fraction = (1/2)^(t/t½)

Baby steps
  1. t½ = 0.693/0.1155 = 6 min.
  2. n = 12/6 = 2 half-lives.
  3. Fraction remaining = (1/2)² = 0.25.

Answer · (a) 0.25

Shortcut · When k looks like a multiple of 0.0693 or 0.1155, converting to t½ first almost always makes the numbers whole.
Q48

If a first order reaction has a rate constant of 10⁻³ s⁻¹, the time needed for the concentration to fall from 0.1 M to 0.025 M is:

Given

k = 10⁻³ s⁻¹, 0.1 M → 0.025 M

Asked

t

Concept

0.1 → 0.025 is a factor of four, i.e. two half-lives.

Formula

t½ = 0.693/k ; t = n·t½

Baby steps
  1. 0.025/0.1 = 1/4, so n = 2 half-lives.
  2. t½ = 0.693/10⁻³ = 693 s.
  3. t = 2 × 693 = 1386 s.

Answer · (a) 1386 s

Q49

For a first order reaction the rate becomes one-eighth of its initial value. The concentration of the reactant at that moment, relative to its initial value, is:

Given

Rate falls to 1/8 of the initial rate

Asked

Relative concentration

Concept

For first order the rate is directly proportional to concentration, so the two fall in step.

Formula

Rate = k[R], so Rate/Rate₀ = [R]/[R]₀

Baby steps
  1. Divide the rate at time t by the initial rate: Rate/Rate₀ = k[R]/k[R]₀ = [R]/[R]₀.
  2. The k cancels, so the ratios are equal.
  3. Rate is 1/8, therefore the concentration is also 1/8 of the original.

Answer · (a) one-eighth

Shortcut · This proportionality is unique to first order. For second order the rate would fall as the square.
Q50

Two first order reactions have half-lives in the ratio 3 : 1. The ratio of their rate constants k₁ : k₂ is:

Given

t½(1) : t½(2) = 3 : 1

Asked

k₁ : k₂

Concept

k and t½ are inversely proportional, so the ratio inverts.

Formula

k = 0.693/t½

Baby steps
  1. k₁ = 0.693/t½(1) and k₂ = 0.693/t½(2).
  2. Divide: k₁/k₂ = t½(2)/t½(1) = 1/3.
  3. So k₁ : k₂ = 1 : 3.

Answer · (a) 1 : 3

Shortcut · Whenever half-lives are given as a ratio, the rate-constant ratio is simply flipped.
Q51

The half-life of a first order reaction is 1.7 hours. The time required for 87.5% completion is:

Given

t½ = 1.7 h, 87.5% completion required

Asked

t

Concept

87.5% gone leaves 12.5% = 1/8, which is exactly three half-lives.

Formula

remaining = (1/2)ⁿ

Baby steps
  1. 100 − 87.5 = 12.5% remains, which is 1/8.
  2. 1/8 = (1/2)³, so n = 3.
  3. t = 3 × 1.7 = 5.1 hours.

Answer · (a) 5.1 hours

Q52PYQ pattern

In a first order reaction, the concentration of the reactant decreases from 800 mol dm⁻³ to 50 mol dm⁻³ in 2 × 10⁴ s. The rate constant is:

Given

800 → 50 mol dm⁻³ in 2 × 10⁴ s

Asked

k

Concept

800/50 = 16, which is four halvings — no logs required.

Formula

t½ = t/n ; k = 0.693/t½

Baby steps
  1. Ratio = 800/50 = 16 = 2⁴, so n = 4 half-lives.
  2. t½ = 2 × 10⁴/4 = 5 × 10³ s.
  3. k = 0.693/5000 = 1.386 × 10⁻⁴ s⁻¹.

Answer · (a) 1.386 × 10⁻⁴ s⁻¹

Shortcut · Always test the concentration ratio against 2, 4, 8, 16, 32 before reaching for logarithms.
Q53

A drug is eliminated from the body by first order kinetics with a half-life of 4 hours. If 200 mg is taken, the amount remaining after 12 hours is:

Given

Initial 200 mg, t½ = 4 h, t = 12 h

Asked

amount remaining

Concept

Pharmacokinetics is first order; the halving ladder applies exactly as in chemistry.

Formula

amount = initial/2ⁿ, n = t/t½

Baby steps
  1. n = 12/4 = 3 half-lives.
  2. 200 → 100 → 50 → 25 mg.
  3. So 25 mg remains.

Answer · (a) 25 mg

Shortcut · Halving step by step is quicker and safer than computing 200/2³ under time pressure.
Q54

For the first order reaction 2N₂O₅ → 4NO₂ + O₂, the half-life at 318 K is 1440 s. The rate constant is:

Given

t½ = 1440 s, first order

Asked

k

Concept

The half-life relation applies regardless of the stoichiometric coefficients, provided the reaction is first order.

Formula

k = 0.693/t½

Baby steps
  1. k = 0.693/1440.
  2. 0.693/1440 = 4.81 × 10⁻⁴ s⁻¹.
  3. Note the coefficient 2 in front of N₂O₅ plays no part here — the half-life relation already refers to the rate constant of the first order decay.

Answer · (a) 4.81 × 10⁻⁴ s⁻¹

Shortcut · Do not multiply or divide by stoichiometric coefficients in a t½ = 0.693/k step. That factor belongs to rate expressions, not to this relation.
Q55

A first order reaction is 40% complete in 50 minutes. What percentage remains after 100 minutes?

Given

40% complete in 50 min

Asked

percentage remaining at 100 min

Concept

Equal time intervals multiply the surviving fraction, so no logarithm is needed.

Formula

remaining after two equal intervals = (fraction per interval)²

Baby steps
  1. After the first 50 min, 60% remains.
  2. After the second 50 min, 60% of that 60% remains.
  3. 0.60 × 0.60 = 0.36, so 36% remains.

Answer · (a) 36%

Shortcut · Whenever the second time is a whole multiple of the first, just raise the surviving fraction to that power.
Q56

The rate constant of a first order reaction at 27 °C is 2.5 × 10⁻³ s⁻¹. The initial concentration is 0.4 M. The initial rate of the reaction is:

Given

k = 2.5 × 10⁻³ s⁻¹, [R]₀ = 0.4 M

Asked

initial rate

Concept

Substitute directly into the differential rate law — no integration needed.

Formula

Rate = k[R]

Baby steps
  1. Rate = 2.5 × 10⁻³ × 0.4.
  2. = 1.0 × 10⁻³ mol L⁻¹ s⁻¹.
  3. Check the units: s⁻¹ × mol L⁻¹ = mol L⁻¹ s⁻¹, which is a proper rate unit.

Answer · (a) 1.0 × 10⁻³ mol L⁻¹ s⁻¹

Shortcut · Reading 'initial rate' should send you to the differential law, not the integrated one.
Q57

A first order reaction has t½ = 30 s. The time in which the reaction is 99% complete is closest to:

Given

t½ = 30 s, 99% completion

Asked

t

Concept

99% completion always takes 6.64 half-lives.

Formula

t₉₉ = 4.606/k and t½ = 0.693/k, so t₉₉ = 6.64 t½

Baby steps
  1. The ratio t₉₉/t½ = 4.606/0.693 = 6.64.
  2. t₉₉ = 6.64 × 30 = 199 s.
  3. Alternatively: k = 0.693/30 = 0.0231 s⁻¹, then t = 4.606/0.0231 = 199 s.

Answer · (a) about 199 s

Q58

For a first order reaction, a plot of [R] against t is drawn. The instantaneous rate at any time equals:

Given

Concentration versus time plot for first order

Asked

Meaning of instantaneous rate on the graph

Concept

Instantaneous rate is a derivative, and a derivative is the slope of the tangent.

Formula

r_inst = −d[R]/dt

Baby steps
  1. The instantaneous rate is defined as −d[R]/dt, the derivative of concentration with respect to time.
  2. Geometrically the derivative at a point is the slope of the tangent drawn at that point.
  3. The minus sign only makes the rate positive; its magnitude is the slope magnitude.
  4. Option (d) describes the average rate, not the instantaneous rate.

Answer · (a) the magnitude of the slope of the tangent at that time

Q59

The half-life of a first order reaction doubles when the initial concentration is halved. The order of the reaction is actually:

Given

t½ doubles when [R]₀ is halved

Asked

true order

Concept

Gap content — use the general-order half-life proportionality.

Formula

t½ ∝ 1/[R]₀^(n−1)

Baby steps
  1. Halving [R]₀ doubled t½, so t½ is inversely proportional to [R]₀ to the first power.
  2. That means the exponent (n − 1) equals 1.
  3. n − 1 = 1 gives n = 2, so the reaction is second order.
  4. Sanity check: for first order t½ would not have changed at all, so it cannot be first order.

Answer · (c) second order

Shortcut · Read the exponent straight off: t½ ∝ [R]₀⁰ is first order, ∝ [R]₀¹ is zero order, ∝ [R]₀⁻¹ is second order.
Q60

A first order reaction proceeds at 25 °C. Which of these changes will alter its half-life?

Given

First order reaction; four proposed changes

Asked

Which changes t½

Concept

t½ depends only on k, and k depends only on temperature (and catalyst), not on concentration.

Formula

t½ = 0.693/k ; k = A e^(−Ea/RT)

Baby steps
  1. Options (b), (c) and (d) all change concentration only, and t½ contains no concentration term. None of them matter.
  2. Option (a) changes T, which changes k through the Arrhenius relation.
  3. A change in k necessarily changes t½ = 0.693/k.
  4. So only raising the temperature alters the half-life.

Answer · (a) Raising the temperature

Shortcut · Only two things change k: temperature and a catalyst. Everything else leaves first order half-life untouched.
Q61

If the initial concentration of a first order reactant is 0.5 M and after 30 minutes it is 0.125 M, the rate constant is:

Given

0.5 M → 0.125 M in 30 min

Asked

k

Concept

0.5 to 0.125 is a factor of four, which is two halvings.

Formula

t½ = t/n ; k = 0.693/t½

Baby steps
  1. 0.125/0.5 = 1/4, so n = 2 half-lives.
  2. t½ = 30/2 = 15 min.
  3. k = 0.693/15 = 0.0462 min⁻¹.

Answer · (a) 0.0462 min⁻¹

Q62

For a first order reaction, if 99.9% completion takes 30 minutes, the half-life is about:

Given

t₉₉.₉ = 30 min

Asked

Concept

99.9% completion is very nearly 10 half-lives.

Formula

t₉₉.₉ = 10 t½ (more precisely 9.97)

Baby steps
  1. Use the standard ratio t₉₉.₉/t½ = 6.909/0.693 ≈ 10.
  2. t½ = 30/10 = 3 minutes.

Answer · (a) about 3 min

Shortcut · Reading the '10 × t½' relation backwards is just as valid as reading it forwards.
Q63

Which of the following statements about a first order reaction is INCORRECT?

Given

Four statements about first order kinetics

Asked

Identify the incorrect one

Concept

For first order the concentration falls exponentially, so the raw [R] versus t plot is curved.

Formula

[R] = [R]₀e^(−kt) — a curve ; ln[R] = ln[R]₀ − kt — a line

Baby steps
  1. Check (b): units s⁻¹ are correct for first order.
  2. Check (c): t½ = 0.693/k has no concentration term, so this is correct.
  3. Check (d): the log form is linear in t, so this is correct.
  4. Check (a): [R] = [R]₀e^(−kt) is an exponential decay curve, not a straight line. A straight [R] vs t plot belongs to zero order. So (a) is the incorrect statement.

Answer · (a) A graph of [R] against t is a straight line

Shortcut · Straight [R] vs t → zero order. Straight ln[R] vs t → first order. Mixing these up is the single most common graph error.
Q64

A first order gas-phase reaction has k = 2.303 × 10⁻³ s⁻¹. The time required for the pressure of the reactant to fall to one-tenth of its initial value is:

Given

k = 2.303 × 10⁻³ s⁻¹, p/p₀ = 1/10

Asked

t

Concept

Pressure works exactly like concentration for a gas at constant temperature and volume.

Formula

t = (2.303/k)·log(p₀/p)

Baby steps
  1. p₀/p = 10, and log 10 = 1.
  2. t = 2.303/(2.303 × 10⁻³) × 1.
  3. The 2.303 cancels, leaving t = 1/10⁻³ = 1000 s.

Answer · (a) 1000 s

Shortcut · When k is given as a multiple of 2.303, expect the 2.303 in the numerator to cancel. That is usually deliberate.
Q65

For a first order reaction with rate constant k, the time at which the concentration falls to 1/e of its initial value is:

Given

[R]/[R]₀ = 1/e

Asked

t

Concept

Taking natural logs makes this a one-line problem — and this time is the mean life.

Formula

[R] = [R]₀e^(−kt)

Baby steps
  1. Set e^(−kt) = 1/e = e⁻¹.
  2. Equate the exponents: −kt = −1.
  3. Therefore t = 1/k, which is exactly the mean life τ.

Answer · (a) 1/k

Shortcut · 1/e ↔ mean life ↔ 1/k. Do not confuse it with 1/2 ↔ half-life ↔ 0.693/k.
Q66

Which pairing of reaction and order is correct according to NCERT?

Given

Four reaction–order pairings

Asked

The correct pairing

Concept

Recall the named examples given in the text.

Formula

Baby steps
  1. N₂O₅ decomposition is quoted in NCERT as a first order reaction, so (a) is correct.
  2. NH₃ on hot platinum at high pressure is the standard zero order example, so (b) is wrong.
  3. Hydrogenation of ethene has Rate = k[C₂H₄], which is first order, so (c) is wrong.
  4. All radioactive decay is first order, so (d) is wrong.

Answer · (a) Decomposition of N₂O₅ — first order

Q67

A first order reaction has k = 0.693 min⁻¹ at a certain temperature. Starting with 1 mol L⁻¹, the concentration after 3 minutes is:

Given

k = 0.693 min⁻¹, [R]₀ = 1 M, t = 3 min

Asked

[R]

Concept

k = 0.693 makes t½ exactly 1 minute, so the elapsed minutes are the number of half-lives.

Formula

t½ = 0.693/k

Baby steps
  1. t½ = 0.693/0.693 = 1 minute.
  2. In 3 minutes, n = 3 half-lives pass.
  3. [R] = 1/2³ = 0.125 mol L⁻¹.

Answer · (a) 0.125 mol L⁻¹

Shortcut · k = 0.693 in any time unit means one half-life per unit of that time. Spot it and the arithmetic disappears.
Q68

The fraction of a first order reactant remaining after a time equal to twice the half-life is:

Given

t = 2 t½

Asked

fraction remaining

Concept

Two halvings.

Formula

fraction = (1/2)ⁿ

Baby steps
  1. n = t/t½ = 2.
  2. Fraction = (1/2)² = 0.25.

Answer · (a) 0.25

Q69

A reaction that is first order in A has its rate measured as 4 × 10⁻³ mol L⁻¹ s⁻¹ when [A] = 0.2 M. The rate constant is:

Given

Rate = 4 × 10⁻³ mol L⁻¹ s⁻¹ at [A] = 0.2 M

Asked

k

Concept

Rearrange the differential rate law.

Formula

k = Rate/[A]

Baby steps
  1. k = (4 × 10⁻³)/0.2.
  2. = 2 × 10⁻² s⁻¹.
  3. Unit check: (mol L⁻¹ s⁻¹)/(mol L⁻¹) = s⁻¹, correct for first order.

Answer · (a) 2 × 10⁻² s⁻¹

Q70

A first order reaction takes 100 minutes to go from 90% remaining to 81% remaining. How long would it take to go from 81% remaining to 72.9% remaining?

Given

90% → 81% takes 100 min

Asked

time for 81% → 72.9%

Concept

For first order, equal fractional drops always take equal times, wherever they occur on the curve.

Formula

t depends only on the ratio [R]₁/[R]₂

Baby steps
  1. First step ratio: 90/81 = 1.111.
  2. Second step ratio: 81/72.9 = 1.111 — identical.
  3. Since the time depends only on the ratio, the second step also takes 100 minutes.

Answer · (a) 100 minutes

Shortcut · This memorylessness is the deepest property of first order kinetics: the reaction never 'knows' how far along it is.
Q71

If the half-life of a first order reaction is 6.93 × 10³ s, the time required for 75% of the reactant to be consumed is:

Given

t½ = 6.93 × 10³ s, 75% consumed

Asked

t

Concept

75% consumed leaves 25% = 1/4, which is exactly two half-lives.

Formula

t₇₅ = 2 t½

Baby steps
  1. Remaining = 25% = 1/4 = (1/2)², so n = 2.
  2. t = 2 × 6.93 × 10³ = 1.386 × 10⁴ s.

Answer · (a) 1.386 × 10⁴ s

Q72

For a first order reaction, the ratio of the time taken for 99.9% completion to that for 90% completion is:

Given

First order

Asked

t₉₉.₉ : t₉₀

Concept

Both times are proportional to the logarithm of the reciprocal remaining fraction.

Formula

t ∝ log([R]₀/[R])

Baby steps
  1. t₉₀: remaining 10%, ratio 10, log = 1.
  2. t₉₉.₉: remaining 0.1%, ratio 1000, log = 3.
  3. Ratio of times = 3 : 1.

Answer · (a) 3 : 1

Shortcut · Ratios of first order completion times are ratios of the number of zeros. 10 → 1, 100 → 2, 1000 → 3.
Q73

The rate constant for a first order reaction is 1.54 × 10⁻³ s⁻¹. Calculate its half-life.

Given

k = 1.54 × 10⁻³ s⁻¹

Asked

Concept

Direct substitution.

Formula

t½ = 0.693/k

Baby steps
  1. t½ = 0.693/(1.54 × 10⁻³).
  2. 0.693/1.54 = 0.45.
  3. t½ = 0.45 × 10³ = 450 s.

Answer · (a) 450 s

Q74

A first order reaction with rate constant k has an initial concentration [R]₀. The concentration at time t is best written as:

Given

First order, initial concentration [R]₀

Asked

Expression for [R] at time t

Concept

Recognise the integrated forms of the three common orders.

Formula

[R] = [R]₀e^(−kt)

Baby steps
  1. Option (b) is the zero order integrated law.
  2. Option (c) is the second order integrated law rearranged.
  3. Option (d) has a positive exponent, which would mean the reactant grows — impossible.
  4. Option (a) is the correct first order form, decaying with time.

Answer · (a) [R]₀e^(−kt)

Shortcut · A positive exponent on a reactant is always wrong. That alone kills one option immediately.
Q75

In a first order reaction, 60% of the reactant decomposes in 40 minutes. The rate constant is nearest to:

Given

60% decomposed in 40 min

Asked

k

Concept

Standard log-form calculation with 40% remaining.

Formula

k = (2.303/t)·log(100/(100−x))

Baby steps
  1. Remaining = 40%, so the ratio is 100/40 = 2.5.
  2. log 2.5 = 0.3979.
  3. k = (2.303/40) × 0.3979 = 0.05758 × 0.3979.
  4. k = 0.0229 min⁻¹.

Answer · (a) 0.0229 min⁻¹

Shortcut · Sanity check: 60% gone in 40 min is a little more than one half-life, so t½ ≈ 30 min and k ≈ 0.693/30 ≈ 0.023. Matches.
Q76

A first order reaction is carried out with a catalyst that doubles the rate constant. The time required for 75% completion will:

Given

k doubles because of a catalyst

Asked

effect on t₇₅

Concept

Every characteristic time for a first order reaction is inversely proportional to k.

Formula

t₇₅ = 1.386/k

Baby steps
  1. t₇₅ = 1.386/k, so t₇₅ ∝ 1/k.
  2. If k is doubled, t₇₅ is halved.
  3. The same reasoning applies to t½, t₉₀ and every other completion time — they all scale together.

Answer · (a) be halved

Shortcut · Doubling k halves every time in this unit at once. You never need to redo the calculation from scratch.