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Understanding the Hydration Thermodynamics of Cationic Quaternary Ammonium and Charge-Neutral Amine Surfactants.

Aqueous solubility and interfacial adsorption of surfactants are important for numerous applications. Using molecular dynamics, we have studied the effect of the type of the polar headgroup (cationic quaternary ammonium and charge-neutral amine) and length of the alkyl tail on the hydration free energy of surfactants in infinite dilution. In addition, we have studied the effect of replacing the terminal methyl group of the alkyl tail with a more polar hydroxyl group on the hydration free energy. Quaternary ammonium surfactants have strongly favorable hydration free energies, whereas charge-neutral amine surfactants have unfavorable hydration free energies. The contribution of the quaternary ammonium group in reducing the hydration free energy is estimated to be as large as ∼63 kBT and that of the charge-neutral amine group to be 3 kBT. Both surfactants and their corresponding alkanes have minima in the free energy at the air-water interface. The quaternary ammonium group contributes to a 6 kBT decrease in the free energy of transfer from air-water interface to bulk aqueous phase (termed henceforth as interface transfer free energy). The amine group, on the other hand, has a net zero interface transfer free energy. The interface transfer free energies of surfactants are both enthalpically and entropically unfavorable. The enthalpic penalty is attributed to the loss of water-water interactions. Interestingly, surfactant molecules gain entropy upon their transfer from the air-water interface to the aqueous phase, but this increase is more than compensated by the loss in the entropy of water molecules, presumably due to the ordering of water molecules around the surfactants. Replacing the terminal methyl group of the alkyl tail with a hydroxyl group in quat surfactants reduces their hydration free energy by 10 kBT, thus making them more soluble in water. Attaching a hydroxyl group to the alkyl tail also inhibits their micelle forming tendency in the bulk aqueous phase. Overall, this work reveals how tuning the molecular characteristics of surfactants can help to achieve the desirable aqueous solubility, interfacial properties, and micellization tendency of surfactants.