Integrated rate law 2026-10-14
An integrated rate law relates concentration to elapsed time after solving a rate equation with an initial condition. Its validity retains the assumptions of the underlying rate law, including fixed rate constants and appropriate stoichiometry. The second-order reaction reciprocal-concentration relation is one example; a different rate equation generally requires a different integrated rate law.[ref]
Second-order reaction 2026-10-14
A second-order reaction has overall order of reaction two: a rate law may depend on , or on with partial orders of reaction one and one. Doubling all relevant reactant concentrations multiplies the reaction rate by four at fixed conditions. This experimentally determined dependence does not establish molecularity or a unique reaction mechanism. For an elementary reaction obeying the law of mass action, molecularity and overall order of reaction agree; a net chemical equation alone cannot establish that the conversion is elementary.[ref]
For the single-concentration model, explicitly choose the disappearance rate convention
Here is the coefficient for loss of A, held fixed at the specified temperature and other conditions. Its subscript labels the chosen observed disappearance rate; it does not imply a pseudo-first-order reaction. Assume a uniformly mixed closed system, fixed volume, and no appreciable reverse or competing chemical reactions. The integrated rate law is
The reciprocal-concentration plot is a straight line with slope and intercept . A brief derivation uses the chain rule: , then applies the initial condition. This is a hyperbolic decay, rather than the exponential decay of a first-order reaction.[ref]
As an original prescribed example, choose and . At , the reciprocal-concentration calculation is , giving . The initial disappearance rate is ; after it is . Halving the concentration quarters the disappearance rate.
Dimensional analysis checks every formula: has units , has units , and is a dimensionless quantity. Changing concentration units changes the numerical rate constant: the same example is , , giving .
Figure 1.
Second-order reaction concentration decay and reciprocal-concentration lines for three prescribed starting concentrations
. Original model curves, not measured data. All use the disappearance rate coefficient . The reciprocal lines share a slope while their intercepts differ; marked points give each run's first half-life. Details.
For an elementary reaction , instead define the stoichiometrically normalized reaction rate . Two A entities disappear per P formed, so
Consequently the reciprocal-concentration slope is , not . In the prescribed example, the normalized rate constant would be ; initially while the disappearance rate is twice that. With , stoichiometry gives . Both rate constants have the same dimensions, so a units check alone cannot catch their factor-of-two difference. The symbol denotes the same normalization as in reaction rate.
The half-life, meaning the time to reach half a specified starting concentration, follows by setting :
For in , this becomes . Its units are seconds because has units . Doubling the starting concentration halves the first half-life; a quoted half-life needs its starting concentration. This differs from a first-order reaction, whose half-life is independent of starting concentration.[ref]
Within the prescribed run, reaches , , and at , , and . The successive halving intervals are , , and : each begins at a smaller concentration. More generally, reaching fraction of the initial concentration, with , requires , so consumption takes nine initial half-lives, rather than a fixed sequence of equal waiting times.
Figure 2.
Lengthening second-order reaction halving intervals and the dependence of the first half-life on initial concentration
. Original model predictions, not measurements. Left: the prescribed run. Right: at fixed , compared with a first-order reaction chosen to have . That comparison uses , with different units from . Details.
A straight reciprocal-concentration plot tests this particular single-concentration rate equation. It does not uniquely identify a reaction mechanism, nor does curvature rule out every second-order reaction: two independently changing reactant concentrations require their own integrated rate law. At low concentration, a small measurement error becomes approximately in the reciprocal, magnifying late-time errors. Use the line as a diagnostic; a nonlinear regression of the original concentrations can retain their measurement scale and explicit error model.