Arrhenius equation 2026-10-13
The Arrhenius equation models the temperature dependence of a rate constant by
Here is the pre-exponential factor, the activation energy, the molar gas constant, and the absolute thermodynamic temperature. In its original form, and are held constant over the range being modeled. It is an empirical relationship, not a universal rule for every reaction mechanism. See the Arrhenius equation.
Eliminating between two positive temperatures gives the useful prediction
For , warming increases . The logarithmic sensitivity is , so there is no universal doubling per ten degrees. The same rise from to gives a factor for , versus for .
Figure 1. . Both models are anchored at , so they have different pre-exponential factors. Left: the higher activation energy produces a larger relative change with temperature. Right: the natural logarithm of the dimensionless ratio is linear in inverse temperature. These exact model curves are not experimental data. Details.
The useful simplification is that a strong change in reaction rate becomes a straight-line relation after changing variables. Measurements at several temperatures can estimate the slope and test whether one pair of constants describes the chosen range. Curvature can indicate a failure of that approximation; fitting a line does not uniquely establish a microscopic reaction mechanism.
Svante Arrhenius's 1889 paper on sucrose conversion through catalysis by a chemical acid compared the strong observed temperature dependence with the much smaller increase in collision frequency. He discussed van't Hoff's earlier temperature relations and proposed a small population of hypothetical active sucrose, replenished from ordinary sucrose, to interpret the dependence. The inspected translated excerpt derives an inverse-temperature relation in its equations (6)–(7) and then applies it to the reaction rate. That historical hypothesis is distinct from a modern transition state description. See the On the Reaction Velocity of the Inversion of Cane Sugar by Acids. The excerpt omits parts of the original paper; it does not provide a complete original apparatus description or dataset.
The pre-exponential factor must have the same units as the rate constant, since the exponential function supplies a dimensionless quantity. For a rate law , both and have units . Thus a first-order reaction uses , whereas a second-order reaction uses . Calling a frequency factor does not give it frequency units for every order of reaction. Its value includes the physical and geometrical factors allowed by the chosen reaction mechanism; equal activation energies need not mean equal reaction rates.
Figure 2. . Both chosen first-order reaction models have and the same exponent parameter . Blue uses a constant pre-exponential factor; orange multiplies it by . All markers are synthetic evaluations, not observations. Left: natural logarithm of against . Right: the corresponding apparent activation energies, and in . The dashed orange tangent at has numerical slope on the displayed horizontal scale. Details.
To read the blue Arrhenius plot, define the dimensionless quantity and . Its numerical slope is , giving . The slope against , by contrast, is . The orange tangent at gives ; its finite-interval slope between and gives about . The distinction between a local derivative and a fitted interval matters even with perfectly noise-free synthetic evaluations.
Two measured positive rate constants give a two-point estimate
Several temperatures let linear regression test the constant-parameter approximation: inspect the regression residuals, keep the same rate law and composition convention, and account for uncertainty in both and . A straight line over a short range supports a useful local approximation; it does not uniquely identify a reaction mechanism. A fixed change of units or of shifts the intercept without changing the inferred activation energy.[ref]