1 Line-by-Line Walkthrough
Read each line, peek at the "Easy idea" box for the friendly version, then commit it to memory before jumping to the tables.
Chemical kinetics is the branch of chemistry that studies how fast a reaction takes place and the factors that govern that speed.
Rate of reaction = change in concentration of a reactant or product per unit time. Average rate uses Δ[A]/Δt; instantaneous rate uses d[A]/dt at a single instant.
For a reaction aA + bB → cC + dD, the unique rate is defined as r = −(1/a) d[A]/dt = −(1/b) d[B]/dt = +(1/c) d[C]/dt = +(1/d) d[D]/dt.
Factors affecting rate: nature of reactants, concentration, temperature, catalyst, surface area, light/radiation.
Rate law / rate expression: rate = k[A]x[B]y. The exponents x, y are found experimentally and are called the orders with respect to A and B. Overall order = x + y.
Rate constant k: proportionality constant in the rate expression. Depends on temperature (and catalyst), NOT on concentration.
Molecularity = number of reacting species (atoms, ions, molecules) that collide simultaneously in an elementary reaction. Always a small whole number (1, 2, rarely 3).
Zero-order reaction: rate = k. Integrated form [A] = [A]₀ − kt. Half-life: t₁/₂ = [A]₀/(2k). Examples: photochemical reactions, decomposition of HI on gold surface.
First-order reaction: rate = k[A]. Integrated: ln[A]/[A]₀ = −kt, or k = (2.303/t) log([A]₀/[A]). Half-life t₁/₂ = 0.693/k (independent of [A]₀).
Pseudo-first-order reaction: When one reactant is in large excess so its concentration appears constant, an actually second-order reaction behaves as first-order. Example: hydrolysis of ester with excess water.
Temperature dependence — Arrhenius equation: k = A·e−Ea/RT. A is the pre-exponential (frequency) factor; Ea is activation energy. Taking ln: ln k = ln A − Ea/(RT). Plot of ln k vs 1/T is straight with slope −Ea/R.
Activation energy (Ea): minimum energy that reactant molecules must possess to give products. The energy "hill" between reactants and products in the energy profile.
Temperature coefficient: ratio k(T+10)/k(T). Typically 2 to 3 for most reactions ⇒ rate doubles or triples per 10 °C rise.
Collision theory: For a reaction, molecules must (i) collide, (ii) with sufficient kinetic energy (E ≥ Ea) and (iii) with proper orientation. Rate = collision frequency × fraction of effective collisions = Z · P · e−Ea/RT.
Catalyst: substance that increases reaction rate without itself being consumed. It works by providing an alternative path of lower activation energy. It does NOT change ΔH, equilibrium position, or Gibbs free energy.
2 Concepts to know for NEET MCQs
| Concept | Key idea | Where it shows up in NEET |
|---|---|---|
| Rate of reaction | Δ[X]/Δt with stoichiometric divisor | "Rate of N₂O₅ disappearance vs O₂ formation" questions |
| Order vs molecularity | Order = experimental; molecularity = mechanistic | "Why pseudo-first order?" "Can order be fractional?" |
| Rate constant k | Depends on T, NOT on concentration | "What affects k?" "Why is k different at different T?" |
| Zero, first, second order | Integrated rate forms & half-life | Numerical PYQs on k or t₁/₂ |
| Pseudo first-order | Excess reagent makes 2nd-order look 1st | Ester hydrolysis, inversion of sugar |
| Arrhenius equation | k = A·e−Ea/RT; ln k vs 1/T linear | Ea calculations from k at two T's |
| Activation energy | Energy hill; ΔH = Ea(forward) − Ea(back) | Energy profile diagrams |
| Collision theory | Z · P · e−Ea/RT | "Why does T raise rate dramatically?" |
| Catalyst | Lowers Ea; doesn't shift equilibrium | "Effect on rate vs equilibrium" trap |
| Temperature coefficient | ~ 2–3 per 10 °C rise | "Rate at 27 °C → 47 °C ratio" PYQs |
3 Formulas Bank
| Quantity | Formula | Notes |
|---|---|---|
| Rate (general) | r = −(1/ν_R) d[R]/dt = +(1/ν_P) d[P]/dt | ν = stoichiometric coefficient |
| Rate law | rate = k [A]x [B]y | x + y = overall order |
| Zero order — integrated | [A] = [A]₀ − k t | k has units of mol L⁻¹ s⁻¹ |
| Zero order — half-life | t₁/₂ = [A]₀/(2k) | Depends on initial concentration |
| First order — integrated | ln [A]/[A]₀ = −kt or k = (2.303/t) log ([A]₀/[A]) | k unit: s⁻¹ (or min⁻¹) |
| First order — half-life | t₁/₂ = 0.693/k | Independent of [A]₀ |
| Second order (single reactant) | 1/[A] − 1/[A]₀ = kt | t₁/₂ = 1/(k[A]₀) |
| Arrhenius | k = A · e−Ea/RT | A = frequency factor |
| Arrhenius (two T) | ln (k₂/k₁) = (Ea/R) · (T₂ − T₁)/(T₁ T₂) | Compute Ea from two k values |
| Arrhenius (log form) | log (k₂/k₁) = (Ea / 2.303 R) · (T₂ − T₁)/(T₁ T₂) | Most common in NEET PYQs |
| Slope of ln k vs 1/T | slope = −Ea / R | Used in Arrhenius plots |
| Effect of catalyst on rate | kcat / k = exp(ΔEa / RT) | ΔEa = drop in activation energy |
| Temperature coefficient | μ = k(T+10) / k(T) | Usually 2 to 3 |
| Fraction with E ≥ Ea | f = e−Ea/RT | Boltzmann factor |
| ΔH from activation energies | ΔH = Ea(forward) − Ea(reverse) | +ve ⇒ endothermic |
4 Facts you must remember
| Fact | Why it matters for NEET |
|---|---|
| Rate constant k depends only on T, not on concentration | Classic MCQ statement; "k changes if…" trap |
| Order of reaction can be 0, fractional, or negative | Conceptual MCQs on order definition |
| Molecularity is always a small whole number (1, 2, rarely 3) | Distinguish from order in MCQs |
| Half-life of first order is independent of initial concentration | Direct PYQ pattern |
| For zero-order: t₁/₂ ∝ [A]₀; for second-order: t₁/₂ ∝ 1/[A]₀ | Recognise order from t₁/₂ vs [A]₀ behaviour |
| Rate doubles for every 10 °C rise (rule of thumb) | Quick PYQ shortcut |
| Arrhenius plot of ln k vs 1/T is a straight line with slope −Ea/R | Direct graph-reading question |
| Catalyst lowers Ea of forward AND reverse equally | Catalyst does NOT shift equilibrium |
| Pseudo-first-order: e.g., ester hydrolysis in excess water, inversion of sugar | Standard NEET fact MCQ |
| Units of k vary with order: (mol L⁻¹)1−n · s⁻¹ | Predict order from units |
| Decomposition of NH₃ on Pt surface, photochemical reactions are zero-order examples | Memorise specific examples |
| Radioactive decay is universally first-order | Common NEET context |
5 Controversial / Confusing Points
| Confusion | Clarification |
|---|---|
| "Is order same as molecularity?" | No. Order = experimental exponent (can be 0/fractional/negative). Molecularity = number of colliding species in the elementary step (small whole number). |
| "Does the rate of forward and reverse change equally with catalyst?" | Yes. Catalyst lowers Ea of both directions by the same amount ⇒ both rates rise but Keq is unchanged. |
| "Does k depend on volume?" | No. Only T (and catalyst). Volume changes concentration, not the rate constant. |
| "Half-life of first order is independent of [A]₀?" | Yes — this is the unique signature of first-order reactions. Use it to identify order. |
| "Can a reaction be zero-order forever?" | No. Zero-order only until the reactant nearly runs out — then mechanism / surface saturation changes. |
| "Is ln k vs T linear?" | No. ln k vs 1/T is linear (Arrhenius); ln k vs T is curved. |
| "Pseudo-first-order has order 1 or 2?" | Observed (experimental) order is 1; true molecularity is 2. |
| "Effective collisions need energy AND orientation?" | Yes — both conditions. P (steric factor) accounts for orientation. |
6 Assumptions in this chapter
| Assumption | When it's invoked |
|---|---|
| Reactions occur in a homogeneous, well-stirred phase | Rate-law writing assumes uniform [A] throughout |
| Activation energy Ea is constant with T (over a small range) | So that ln k vs 1/T is linear (Arrhenius) |
| Reverse reaction is negligible at the start | Allows simple integrated rate laws (no equilibrium correction) |
| Pre-exponential factor A is independent of T | Strictly A ∝ √T, but assumed constant in basic Arrhenius |
| Reactant in large excess stays essentially constant | Justifies "pseudo-first-order" treatment |
| Elementary steps follow simple collision mechanics | Underlies the collision theory derivation |
| Gases behave ideally; solutions are dilute | So concentrations are well-defined and additive |
| Catalyst's surface area is constant during reaction | So that observed kinetics reflect a single mechanism |
7 Exceptions to remember
| Rule | Exception / Special case |
|---|---|
| Rate ∝ concentration of every reactant | Zero-order reactions ignore concentration entirely (e.g., NH₃ on Pt) |
| Order = sum of stoichiometric coefficients | False in general; only true for elementary reactions |
| Order is a positive integer | Can be fractional (e.g., 0.5 for H₂ + Br₂ → 2HBr) or even negative |
| Rate always increases with T | Some enzyme reactions decrease at high T due to denaturation; some explosive reactions show non-monotonic behaviour |
| Arrhenius plot is linear | Curved for complex mechanisms or wide T ranges |
| t₁/₂ of first order is independent of [A]₀ | Only true if the reaction stays first-order (no surface saturation) |
| Catalyst doesn't appear in stoichiometric equation | Auto-catalysis — a product accelerates the reaction (e.g., HNO₂ in oxidation of As₂O₃) |
| Temperature coefficient ≈ 2 | For some enzyme-catalysed and explosive reactions can be 10⁶ or near 1 |
8 Scientists and years
| Scientist | Year | Contribution |
|---|---|---|
| Ludwig Wilhelmy | 1850 | First quantitative kinetic study — sucrose inversion rate |
| Peter Waage & Cato Guldberg | 1864 | Law of mass action — basis of rate law |
| Jacobus van 't Hoff | 1884 | Studies on reaction order and rate; thermodynamic equation for K vs T |
| Svante Arrhenius | 1889 | Arrhenius equation; concept of activation energy |
| Max Trautz / William Lewis | 1916–1918 | Collision theory of bimolecular gas reactions |
| Henry Eyring | 1935 | Transition-state theory (absolute rate theory) |
| Berzelius | 1835 | Coined the term "catalyst" |
| Wilhelm Ostwald | 1894 | Modern definition of catalyst; Nobel Prize 1909 for catalysis |
9 NEET Traps to avoid
| Trap | How to avoid it |
|---|---|
| Confusing order with molecularity | Order = experimental, can be 0/fractional/negative. Molecularity = elementary-step species count, small whole number. |
| Writing rate law directly from balanced equation | Only for elementary reactions. Otherwise rate law is found by experiment. |
| Mis-applying t₁/₂ formula across different orders | Remember which depends on [A]₀: only zero-order t₁/₂ ∝ [A]₀; first-order independent; second-order ∝ 1/[A]₀. |
| Forgetting the 2.303 factor when using log instead of ln | k = (2.303/t) log ratio for first order — drop the 2.303 only if using ln. |
| Saying catalyst shifts equilibrium | Catalyst speeds both sides equally — equilibrium position unchanged. |
| Confusing slope of ln k vs 1/T sign | Slope = −Ea/R. Negative slope ⇒ positive Ea (normal). |
| Mixing T₂ − T₁ direction in Arrhenius equation | Write as (T₂ − T₁)/(T₁T₂) with T₂ > T₁ so the result is positive when rate increases. |
| Forgetting units of k change with order | k unit = (mol L⁻¹)1−n · time⁻¹. |
| Calling photochemical reactions "complex" | They're often zero-order because rate depends on light intensity, not concentration. |
| Assuming Arrhenius plot is straight always | Only over a small T range and for a single mechanism. |
📊 Diagrams
a) Concentration vs time (instantaneous rate)
Slope of the tangent at any instant = instantaneous rate (−d[A]/dt).
b) Activation energy / energy profile
Ea is the "hill" reactants must climb to form the activated complex. ΔH is the net energy drop to products.
c) Arrhenius plot — ln k vs 1/T
Straight line with slope = −Ea/R. Intercept = ln A.
d) Maxwell–Boltzmann energy distribution at two temperatures
Higher T flattens the curve — more molecules cross the activation threshold (area to the right of Ea grows).
e) Effect of catalyst on activation energy
Dashed path = with catalyst (lower Ea). Same start and end heights (no change in ΔH).
f) Linear plots that identify reaction order
Zero-order: [A] vs t straight. First-order: ln[A] vs t straight. Second-order: 1/[A] vs t straight.
📝 50 PYQs — 25 NEET + 25 JEE Main
Each question shows the easy idea, given data, what to find, formula and a clean step-by-step solution. Tap a card to expand.