Arrhenius equation 2026-10-13
The Arrhenius equation models the temperature dependence of a rate constant byHere 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 predictionFor , 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 .
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.
Synthetic Arrhenius plots: a constant pre-exponential factor and a temperature-dependent pre-exponential factor
. 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 estimateSeveral 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]
12.5 Collision Theory. §12.5, Example 12.13 and alternate two-point approach: estimating activation energy from a slope
Electrolyte Created 2026-10-06 Updated 2026-10-13
An electrolyte is a conducting medium in which mobile ions carry electric current, according to IUPAC Gold Book: electrolyte. In introductory chemistry, a substance that yields ions when dissolved in water is also called an electrolyte. Both usages point to the same mechanism: an electric field gives mobile cations and anions directed drift velocities.
Mobility matters as much as the presence of electric charge. In a simple ideal model of solid sodium chloride, ions are confined to their sites and do not carry a sustained transport electric current. Molten sodium chloride has mobile ions; dissolved sodium chloride gives mobile and ions in water. Real solids can have some ionic transport through imperfections; the immobile-solid picture is an introductory limit, rather than a claim that all solids are perfect insulators.
A strong electrolyte yields essentially all ions from the dissolved substance, whereas a weak electrolyte yields only a fraction under the specified conditions. Dissolved sodium chloride is a strong electrolyte. Sucrose is a nonelectrolyte: it dissolves as neutral molecules, so dissolving something does not automatically create mobile ions. Water's own small population of hydronium and hydroxide remains possible. See 11.2 Electrolytes (§11.2: strong, weak, and nonelectrolytes) and Flowers et al., Chemistry 2e, §11.4, Table 11.3: sucrose and sodium chloride.
Acetic acid is a weak electrolyte and a weak acid. In water, some neutral acetic acid molecules transfer a proton to water, producing hydronium and the negatively charged partner:Both sides have net electric charge zero. At chemical equilibrium, neutral acetic acid coexists with these ions; the fraction converted depends on the conditions. Electrolyte strength describes this extent of ion production, while concentration describes how much substance is present per specified quantity of chemical solution. A dilute strong electrolyte can contain fewer ions per volume than a concentrated weak electrolyte. Neither the words strong and weak nor a conductivity comparison alone specifies concentration.
Now specify an electrolytic cell with a positive anode on the left, a negative cathode on the right, and an approximately uniform electric field pointing right in the bulk electrolyte. With a steady external source and neglecting diffusion and convection, positive cations drift right toward the negative cathode; negative anions drift left toward the positive anode. Yet both populations contribute a rightward conventional current! For number densities and drift velocities , the transport current density isThe product of electric charge and velocity determines conventional current: for the anion, both the charge and its rightward velocity component are negative, making its rightward contribution positive. This is the same sign rule used for Electron conventional current. It follows directly from the existing charge carrier formula.
Opposite ion drift velocities contribute to the same conventional current in a specified electrolytic cell
. The positive anode is left and the negative cathode right. The upper arrows show ion motion; the lower arrows show the signs of for current density. A uniform bulk electric field is assumed; diffusion, convection, and electrode boundary layers are omitted. Arrow lengths are schematic. Details.For an independent numerical example, stipulate , , and . With the exact elementary charge , the contributions areEqual number densities of singly charged cations and anions give zero bulk charge density, while their motion gives nonzero current density. This is why a neutral electrolyte can conduct. These numbers are chosen toy inputs, not measurements of sodium chloride; maintaining sustained cell electric current also requires suitable electrode reactions. Blocking electrodes can instead lead to charge accumulation and decay of the electric current.
An electrolyte connects the microscopic motion of ions to observable electrical conductivity. A counterion-only model keeps just the mobile counterions needed to oppose a fixed electric charge; Poisson-Boltzmann equations use ideal Boltzmann distributions to model their equilibrium distributions, rather than the drift example above.
Nonelectrolyte 2026-10-13
Sucrose 2026-10-13


