Integrated Rate Laws

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zero-order first-order second-order half-life integrated-rate-law graphical-method concentration-vs-time

Core Idea

Integrated rate laws relate concentration to time, enabling prediction of how much reactant remains after a given period. For a reaction A → products: zero order gives [A] = [A]₀ − kt (linear in [A] vs t); first order gives ln[A] = ln[A]₀ − kt (linear in ln[A] vs t, half-life t₁/₂ = 0.693/k); second order gives 1/[A] = 1/[A]₀ + kt (linear in 1/[A] vs t). The graphical method determines order experimentally: plot [A], ln[A], and 1/[A] against time, and whichever gives a straight line reveals the order. Half-life for first-order reactions is uniquely concentration-independent.

How It's Best Learned

Memorize the three integrated forms and their corresponding straight-line plots. Practice determining order from graphical data — the linear plot identifies the order, the slope gives k (with appropriate sign). Work half-life problems for each order and notice how only first-order half-life is constant (radioactive decay is the classic example).

Common Misconceptions

Explainer

From chemical kinetics, you know that rate laws express how reaction speed depends on concentration: rate = k[A]ⁿ, where n is the reaction order. But rate laws in that form tell you the instantaneous speed at a given moment — they don't directly answer the practical question "how much reactant is left after 30 minutes?" That's what integrated rate laws answer. They are the mathematical result of integrating the differential rate law over time, converting a statement about speed into a statement about concentration as a function of time.

For a zero-order reaction (rate = k, independent of concentration), integration gives [A] = [A]₀ − kt. Concentration decreases linearly with time, like a faucet draining at a constant rate regardless of how much water remains. The half-life is t₁/₂ = [A]₀/2k — it depends on starting concentration, so each successive half-life is shorter. For a first-order reaction (rate = k[A]), integration gives ln[A] = ln[A]₀ − kt, or equivalently [A] = [A]₀e⁻ᵏᵗ. This is exponential decay — the same mathematics that governs radioactive decay, which is why radioactive half-life is constant: t₁/₂ = 0.693/k, independent of how much material remains. For a second-order reaction (rate = k[A]²), integration gives 1/[A] = 1/[A]₀ + kt. The reaction slows dramatically as concentration drops, and the half-life t₁/₂ = 1/(k[A]₀) increases with each successive halving.

The graphical method is the experimental technique for determining reaction order. You measure concentration at several time points, then make three plots: [A] vs t, ln[A] vs t, and 1/[A] vs t. Whichever plot gives a straight line reveals the order — linear in [A] means zero-order, linear in ln[A] means first-order, linear in 1/[A] means second-order. The slope of the straight-line plot gives you the rate constant k (negative slope for zero and first order, positive for second order). This is why the integrated rate laws are written in y = mx + b form: they are designed to be linearized for graphical analysis.

A practical detail worth internalizing: first-order kinetics are by far the most common in chemistry and biology. Drug metabolism, radioactive decay, and many decomposition reactions follow first-order kinetics. The constant half-life property makes first-order processes especially intuitive — if a drug's half-life is 4 hours, then after 4 hours half remains, after 8 hours a quarter remains, after 12 hours an eighth remains, regardless of the initial dose. When a reaction involves multiple reactants, the pseudo-first-order technique simplifies analysis: flood one reactant in large excess so its concentration barely changes, and the rate law reduces to a first-order dependence on the other reactant.

Practice Questions 5 questions

Prerequisite Chain

Counting to 10Counting to 20Understanding ZeroThe Number ZeroCounting to FiveOne-to-One CorrespondenceCombining Small Groups Within 5Addition Within 10Addition Within 20Two-Digit Addition Without RegroupingTwo-Digit Addition with RegroupingAddition Within 100Repeated Addition as MultiplicationMultiplication Facts Within 100Division as Equal SharingDivision as Grouping (Measurement Division)Division: Grouping (Repeated Subtraction) ModelDivision: Fair Sharing ModelDivision as Equal SharingDivision as GroupingBasic Division FactsDivision Facts Within 100Two-Digit by One-Digit DivisionDivision with RemaindersRemainders and Quotients in DivisionDivision Word ProblemsIntroduction to Long DivisionFactors and MultiplesPrime and Composite NumbersEquivalent FractionsRelating Fractions and DecimalsDecimal Place ValueReading and Writing DecimalsComparing and Ordering DecimalsAdding and Subtracting DecimalsMultiplying DecimalsDividing DecimalsDividing FractionsMixed Number ArithmeticOrder of OperationsInteger Order of OperationsVariable ExpressionsCombining Like TermsOne-Step EquationsTwo-Step EquationsSolving Multi-Step EquationsEquations with Variables on Both SidesAngle Pairs: Complementary, Supplementary, and VerticalParallel Lines and TransversalsCorresponding AnglesAlternate Interior AnglesTriangle Angle Sum TheoremExterior Angle TheoremTriangle Inequality TheoremSimilar Triangles: AA SimilaritySimilar Triangles: SSS and SAS SimilarityProportions in Similar TrianglesRight Triangle Trigonometry IntroductionTrigonometric Ratios ReviewRadian MeasureConverting Between Degrees and RadiansThe Unit CircleGraphing Sine and CosineGraphing Tangent and Reciprocal Trigonometric FunctionsDerivatives of Trigonometric FunctionsAntiderivativesIterated Integrals and Fubini's TheoremDouble Integrals in Cartesian CoordinatesDouble Integrals over Rectangular RegionsDouble Integrals in Polar CoordinatesDouble Integrals: Definition and SetupIterated Integrals and Fubini's TheoremDouble Integrals over Rectangular RegionsDouble Integrals over General RegionsApplications of Double Integrals: Area, Mass, and MomentsTriple Integrals in Cartesian CoordinatesTriple Integrals in Cylindrical and Spherical CoordinatesChange of Variables and the Jacobian DeterminantApplications of Triple Integrals: Volume and MassVector Fields and Their RepresentationsLine Integrals of Vector FieldsGreen's TheoremSurface Integrals and Flux of Vector FieldsSurface Integrals and Flux of Vector FieldsDivergence Theorem: Flux and OutflowDivergence TheoremElectric FluxGauss's LawConductors in Electrostatic EquilibriumCapacitance and CapacitorsDielectricsDielectric Constant and Relative PermittivityElectric Field Inside Dielectric MaterialsDielectric Materials and PolarizationDielectric Susceptibility and PermittivityEnergy Density in Electric FieldsElectric Current and Current DensityElectrical Resistance and ResistivityOhm's Law and Circuit ElementsElectromotive Force (EMF) and BatteriesKirchhoff's Circuit Laws: Voltage and CurrentDC Circuit Network Analysis MethodsTransient Response in RC CircuitsRC CircuitsLC and RLC CircuitsAC Circuits: FundamentalsImpedance and ReactanceAC Power and ResonanceElectromagnetic WavesThe Electromagnetic SpectrumBlackbody Radiation and Planck's LawPhotoelectric EffectThe Photon: Light as QuantaCompton ScatteringWave-Particle Dualityde Broglie WavelengthHeisenberg Uncertainty PrincipleWavefunction and the Born RuleThe Schrödinger EquationState Vectors and WavefunctionsQuantum SuperpositionQuantum EntanglementBell Theorem and Bell InequalitiesPostulates of Quantum MechanicsScattering TheoryIntroduction to Scattering TheoryPartial Wave Analysis in ScatteringSpin Angular MomentumElectron Spin and Intrinsic Magnetic MomentStern-Gerlach Experiment: Spin Quantization and MeasurementElectron Diffraction and Matter Wave PropertiesDavisson-Germer Experiment: Crystal Diffraction of ElectronsElectron Diffraction and Matter Wave InterferenceWavefunctions and Probability Density InterpretationQuantum Superposition and Linear Combinations of StatesQuantum Operators and ObservablesCanonical Commutation Relations and UncertaintyHeisenberg Uncertainty Principle and Measurement LimitsTime-Independent Schrödinger Equation and EigenvaluesHydrogen Atom in Quantum MechanicsSpectral Lines and Energy TransitionsSelection Rules for Atomic TransitionsLS and jj Coupling Schemes in Multi-Electron AtomsPauli Exclusion Principle and Antisymmetric WavefunctionsElectron Configuration and the Aufbau PrincipleThe Periodic Table and Atomic Electronic StructureThe Periodic TableElectron ConfigurationPeriodic TrendsIonization EnergyIonic BondingLewis StructuresResonance Structures and Delocalized ElectronsResonance and Formal ChargeMolecular Polarity and Dipole MomentsIntermolecular ForcesStates of Matter and Phase Changes: Melting, Boiling, and SublimationGas Laws and the Ideal Gas EquationGas Stoichiometry and Volume-Volume CalculationsThermochemistry and EnthalpyHeat Capacity and CalorimetryEntropy and Molecular DisorderSpontaneity and ΔGEntropy and Gibbs Free EnergyChemical EquilibriumChemical KineticsIntegrated Rate Laws

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