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Solubility of Butyl Paraben in Methanol, Ethanol, Propanol, Ethyl Acetate, Acetone, and Acetonitrile
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Transport Phenomena.
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Transport Phenomena.
2010 (English)In: Journal of Chemical and Engineering Data, ISSN 0021-9568, E-ISSN 1520-5134, Vol. 55, no 11, 5091-5093 p.Article in journal (Refereed) Published
Abstract [en]

The solubility of butyl paraben (butyl 4-hydroxybenzoate) have been determined in methanol, ethanol, propanol, acetone, ethyl acetate, and acetonitrile in the temperature range of (10 to 50) C by the gravimetric method. The order of the solubility of butyl paraben in the different solvents as mass fraction at 20 C is: methanol > ethanol > acetone > propanol > ethyl acetate > acetonitrile. In terms of mole fraction solubility, the corresponding order is acetone > propanol > ethanol > ethyl acetate > methanol > acetonitrile, which shows that both nonpolar and polar groups of the paraben molecule influence the solubility in the different solvents.

Place, publisher, year, edition, pages
2010. Vol. 55, no 11, 5091-5093 p.
Keyword [en]
published literature, thermodynamics, health
National Category
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-27367DOI: 10.1021/je1006289ISI: 000284017600083Scopus ID: 2-s2.0-78449307514OAI: oai:DiVA.org:kth-27367DiVA: diva2:377372
Note
QC 20101214Available from: 2010-12-14 Created: 2010-12-13 Last updated: 2017-12-11Bibliographically approved
In thesis
1. Investigations intothe crystallization of butyl paraben
Open this publication in new window or tab >>Investigations intothe crystallization of butyl paraben
2011 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

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.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. x, 65 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2011:43
Keyword
Butyl paraben, Solubility, Thermodynamic, Activity, Activity coefficient, Second order correlation, Liquid-liquid phase separation, Ternary phase diagram, Nucleation, Induction time, Free energy, Interfacial energy, Nuclei critical radius Cooling crystallization, Evaporation crystallization
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-34051 (URN)978-91-7501-028-1 (ISBN)
Presentation
2011-06-10, K2, Teknikringen 28, KTH, Stockholm, 16:20 (English)
Opponent
Supervisors
Note
QC 20110630Available from: 2011-06-30 Created: 2011-05-24 Last updated: 2012-03-28Bibliographically approved
2. Crystallization of Parabens: Thermodynamics, Nucleation and Processing
Open this publication in new window or tab >>Crystallization of Parabens: Thermodynamics, Nucleation and Processing
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this work, the solubility of butyl paraben in 7 pure solvents and in 5 different ethanol-water mixtures has been determined from 1 ˚C to 50 ˚C. The solubility of ethyl paraben and propyl paraben in various solvents has been determined at 10 ˚C. The molar solubility of butyl paraben in pure solvents and its thermodynamic properties, measured by Differential Scanning Calorimetry, have been used to estimate the activity of the pure solid phase, and solution activity coefficients.

More than 5000 nucleation experiments of ethyl paraben, propyl paraben and butyl paraben in ethyl acetate, acetone, methanol, ethanol, propanol and 70%, 90% ethanol aqueous solution have been performed. The induction time of each paraben has been determined at three different supersaturation levels in various solvents. The wide variation in induction time reveals the stochastic nature of nucleation. The solid-liquid interfacial energy, free energy of nucleation, nuclei critical radius and pre-exponential factor of parabens in these solvents have been determined according to the classical nucleation theory, and different methods of evaluation are compared. The interfacial energy of parabens in these solvents tends to increase with decreasing mole fraction solubility but the correlation is not very strong. The influence of solvent on nucleation of each paraben and nucleation behavior of parabens in each solvent is discussed. There is a trend in the data that the higher the boiling point of the solvent and the higher the melting point of the solute, the more difficult is the nucleation. This observation is paralleled by the fact that a metastable polymorph has a lower interfacial energy than the stable form, and that a solid compound with a higher melting point appears to have a higher solid-melt and solid-aqueous solution interfacial energy.

It has been found that when a paraben is added to aqueous solutions with a certain proportion of ethanol, the solution separates into two immiscible liquid phases in equilibrium. The top layer is water-rich and the bottom layer is paraben-rich. The area in the ternary phase diagram of the liquid-liquid-phase separation region increases with increasing temperature. The area of the liquid-liquid-phase separation region decreases from butyl paraben, propyl paraben to ethyl paraben at the constant temperature.

Cooling crystallization of solutions of different proportions of butyl paraben, water and ethanol have been carried out and recorded using the Focused Beam Reflectance Method, Particle Vision and Measurement, and in-situ Infrared Spectroscopy. The FBRM and IR curves and the PVM photos track the appearance of liquid-liquid phase separation and crystallization. The results suggest that the liquid-liquid phase separation has a negative influence on the crystal size distribution. The work illustrates how Process Analytical Technology (PAT) can be used to increase the understanding of complex crystallizations.

By cooling crystallization of butyl paraben under conditions of liquid-liquid-phase separation, crystals consisting of a porous layer in between two solid layers have been produced. The outer layers are transparent and compact while the middle layer is full of pores. The thickness of the porous layer can reach more than half of the whole crystal. These sandwich crystals contain only one polymorph as determined by Confocal Raman Microscopy and single crystal X-Ray Diffraction. However, the middle layer material melts at lower temperature than outer layer material.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. xvi, 67 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:20
Keyword
Nucleation, Induction time, Interfacial energy, Ethyl paraben, Propyl paraben, Butyl paraben, Methanol, Ethanol, Propanol, Acetone, Ethyl acetate, Solubility, Thermodynamics, Activity, Activity coefficient, Liquid-liquid phase separation, Ternary phase diagram, Melting point, Boiling point, Polarity, Cooling crystallization, Sandwich crystal, Porous, Particle Vision and Measurement, Focused Beam Reflectance Method, Infrared Spectroscopy, Confocal Raman Microscopy, X-Ray Diffraction, Differential Scanning Calorimetry
National Category
Pharmaceutical Sciences Organic Chemistry Physical Chemistry
Research subject
SRA - E-Science (SeRC)
Identifiers
urn:nbn:se:kth:diva-122228 (URN)978-91-7501-723-5 (ISBN)
Public defence
2013-05-30, K1, Teknikringen 56, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Projects
investigate nucleation and crystallization of drug-like organic molecules
Funder
Swedish e‐Science Research Center
Note

QC 20130515

Available from: 2013-05-15 Created: 2013-05-14 Last updated: 2013-05-15Bibliographically approved

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