Characterization of aquifers contaminated by petroleum hydrocarbons is limited by the use of dissolution mass transfer correlations developed for single compounds without considering the effects of the mass transfer limitations in presence of other components. A one-dimensional implicit numerical model is developed for the coupled mass transfer and transport processes and the results are analysed using existing mass transfer correlations for better understanding of the single and multicomponent dissolution processes. The mass transfer coefficient in the multicomponent system is found to be more nonlinear and extending with changing slope, unlike the exponential reduction for single compound system. During the initial phase, the dissolution rate of a soluble compound is very high due to the high concentration gradient, and as dissolution progresses, its effective solubility decreases with change in mole fraction. At higher pore volumes, the mole fractions of lower solubility fractions increase which can result in higher effective solubility. The kinetics of interphase mass transfer by dissolution and sorption is favoured by coupled biodegradation. However, mass transfer limitation for more soluble compounds under the conditions of low residual saturation and low mole fraction is observed to be due to low dissolution rate coefficient rather than decreasing concentration gradient. © 2014, Indian Academy of Sciences.