Effect of Association of Bromophenol Blue with Tween Surfactants on Its Acid-Base Equilibria at High pH

Abstract

The acid base equilibria of the sulfonephthalein dye bromophenol blue (BPB) in aqueous nonionic micellar solutions of Tween 20, Tween 40, Tween 60, and Tween 80 have been investigated spectroscopically using a partition equilibrium method. A visible red shift in the absorbance of the basic form of the dye with increase in surfactant concentration was observed at and above pH 6.98. This has been attributed to the stabilization of the acid form of the dye by the POE groups on the head of the surfactant monomers. Such stabilization effect was found to decreases with decrease in the number of carbon atom in the hydrophobic tail and with the increase in the hydrophile-lipophile balance (HLB) of the surfactant molecule. The equilibrium constant of the partition of the dyes between micellar and aqueous pseudophases (K_ass) was found to increase with the surfactants in the order Tween 80 < Tween 60 < Tween 40 < Tween 20. The pK_a2 of the dyes were predicted and found to be in good agreement with the experimental values.

Keywords:

• Acid-base equilibrium
• bromophenol blue
• red shift
• tween surfactant

Notes

*pK_a2,m are determined at 298 K and in presence of surfactant with concentration {[S] = 5 × 10⁻³ mol dm⁻³} sufficient to bind all dye molecules.

*Experimental error limits: (±0.2 × 10⁻⁵ mol dm⁻³) for CMC and (±5%) for K_ass.

^a CMC determined from surface tension data.