The kinetics of solute adsorption at the solid/solution interface has been studied by statistical rate theory (SRT) at two limiting conditions, one at initial times of adsorption and the other close to equilibrium. A new kinetic equation has been derived for initial times of adsorption on the basis of SRT. For the first time a theoretical interpretation based on SRT has been provided for the modified pseudo-first-order (MPFO) kinetic equation which was proposed empirically by Yang and Al-Duri. It has been shown that the MPFO kinetic equation can be derived from the SRT equation when the system is close to equilibrium. On the basis of numerically generated points (t, q) by the SRT equation, it has been shown that we can apply the new equation for initial times of adsorption in a larger time range in comparison to the previous q vs root t linear equation. Also by numerical analysis of the generated kinetic data points, it is shown that application of the MPFO equation for modeling of whole kinetic data causes a large error for the data at initial times of adsorption. The results of numerical analysis are in perfect agreement with our theoretical derivation of the MPFO kinetic equation from the SRT equation. Finally, the results of the present theoretical study were confirmed by analysis of an experimental system.