Investigations intothe crystallization of butyl paraben

In thisproject, solubility of butyl paraben in 7 puresolvents and 5 ethanol aqueous solvents has been determined at from 1 ℃to 50 ℃. Thermodynamic properties of butyl paraben have been measured by DifferentialScanning Calorimetey. Relationship between molar solubility of butyl paraben in6 pure solvents and thermodynamic properties has been analyzed. Thisrelationship suggests a method of estimating activity of solute at equilibrium fromcombining solubility data with DSC measurements. Then, activity coefficient accordingto the solubility at different temperatures can be estimated. Duringthe solubility measurements in ethanol aqueous solvents, it is found that whenbutyl paraben is added into aqueous solutions with certain proportion ethanol,solutions separates into two immiscible liquid layers in equilibrium. Water andethanol are primary in top layer, while the butyl paraben is primary in bottomlayer, but the solution turns to cloudy when two layers of solution are mixed. Theaim of this work was to present the phase behaviour of liquid-liquid-phaseseparation for (butyl paraben + water + ethanol) ternary system from 1 ℃ to 50 ℃at atmospheric pressure. Thearea of liquid-liquid-phase separation region in the ternary phase diagram increaseswith the increasing temperature from 10 ℃to 50 ℃. In thisstudy, more than several hundreds of nucleation experiments of butyl paraben havebeen investigated in ethyl acetate, propanol, acetone and 90% ethanol aqueoussolution. Induction time of butyl paraben has been determined at 3 differentsupersaturation levels in these solvents, respectively. Free energy ofnucleation, solid-liquid interfacial energy, and nuclei critical radius havebeen determined according to the classical nucleation theory. Statistical analysis ofinduction time reveals that the nucleation is a stochastic process with widevariation even at the same experiment condition. Butyl paraben nucleates most difficultlyin 90 % ethanol than in other 3 solvents, and most easily in acetone. The interfacialenergy of butyl paraben in these solvents tends to increasing with decreasemole fraction solubility in these solvents. Coolingcrystallizations with different proportions of butyl paraben, water and ethanolhave been observed by Focused Beam Reflectance Method, Parallel VirtualMachine, and On-line Infrared. The FBRM, IR curves and the PVM photos show someof the solutions appeared liquid-liquid phase separation during coolingcrystallization process. The results suggest that if solutions went throughliquid-liquid phase separation region during the cooling crystallizationprocess the distribution of crystals crystal was poor. Droplets from solutions withsame proportion butyl paraben but different proportions of water and ethanolhave been observed under microscope. Induction time of the droplets has been determinedunder the room temperature. Droplets from top layer or bottom layer of solutionwith liquid-liquid phase separation on small glass or plastic plates were alsoobserved under microscope. The microscope photos show that the opposite flows ofcloudy solution on the glass and the plastic plate before nucleation. The resultsof the cooling and evaporation crystallization experiments both revealed thatnucleation would be prevented by the liquid-liquid phase separation.QC 2011063