Abstract: This work focused on the interactions which occur between ester solvents and alcohol solutes. The alcohols selected ranged from the simplest alcohol (methanol) to C10-alcohols, and solubility predictions in the form of infinite dilution activity coefficients were made using the Modified UNIFAC Dortmund group contribution model. The model computation was set up on a Microsoft Excel spreadsheet specifically designed for this purpose. It was found that alcohol/ ester interactions yielded an increase in activity coefficients (i.e. became less soluble) with an increase in the size of the ester solvent molecule. Furthermore, activity coefficients decreased with an increase in the size of the alcohol solute. The activity coefficients also decreased with an increase in the degree of unsaturation of the ester hydrocarbon tail. Tertiary alcohols yielded lower activity coefficients than primary alcohols. Finally, cyclic alcohols yielded higher activity coefficients than straight-chain alcohols until a point is reached where the trend is reversed, referred to as the ‘crossover’ point.
Abstract: Group contribution methods such as the UNIFAC are
very useful to researchers and engineers involved in synthesis,
feasibility studies, design and optimization of separation processes.
They can be applied successfully to predict phase equilibrium and
excess properties in the development of chemical and separation
processes. The main focus of this work was to investigate the
possibility of absorbing selected volatile organic compounds (VOCs)
into polydimethylsiloxane (PDMS) using three selected UNIFAC
group contribution methods. Absorption followed by subsequent
stripping is the predominant available abatement technology of
VOCs from flue gases prior to their release into the atmosphere. The
original, modified and effective UNIFAC models were used in this
work. The thirteen selected VOCs that have been considered in this
research are: pentane, hexane, heptanes, trimethylamine, toluene,
xylene, cyclohexane, butyl acetate, diethyl acetate, chloroform,
acetone, ethyl methyl ketone and isobutyl methyl ketone. The
computation was done for solute VOC concentration of 8.55x10-8
which is well in the infinite dilution region. The results obtained in
this study compare very well with those published in literature
obtained through both measurements and predictions. The phase
equilibrium obtained in this study show that PDMS is a good
absorbent for the removal of VOCs from contaminated air streams
through physical absorption.
Abstract: Isobaric vapor-liquid equilibrium measurements are reported for the binary mixtures of n-Butylamine and Triethylamine with Cumene at 97.3 kPa. The measurements have been performed using a vapor recirculating type (modified Othmer's) equilibrium still. The binary mixture of n-Butylamine + Cumene shows positive deviation from ideality. Triethylamine + Cumene mixture shows negligible deviation from ideality. None of the systems form an azeotrope. The activity coefficients have been calculated taking into consideration the vapor phase nonideality. The data satisfy the thermodynamic consistency test of Herington. The activity coefficients have been satisfactorily correlated by means of the Margules, NRTL, and Black equations. The activity coefficient values obtained by the UNIFAC model are also reported.
Abstract: It is shown that a modified UNIFAC model can be
applied to predict solubility of hydrocarbon gases and vapors in
hydrocarbon solvents. Very good agreement with experimental data
has been achieved. In this work we try to find best way for predicting
dimethyl ether solubility in liquid paraffin by using group
contribution theory.
Abstract: This work considered the thermodynamic feasibility
of scrubbing volatile organic compounds into biodiesel in view of
designing a gas treatment process with this absorbent. A detailed
vapour – liquid equilibrium investigation was performed using the
original UNIFAC group contribution method. The four biodiesels
studied in this work are methyl oleate, methyl palmitate, methyl
linolenate and ethyl stearate. The original UNIFAC procedure was
used to estimate the infinite dilution activity coefficients of 13
selected volatile organic compounds in the biodiesels. The
calculations were done at the VOC mole fraction of 9.213x10-8. Ethyl
stearate gave the most favourable phase equilibrium. A close
agreement was found between the infinite dilution activity coefficient
of toluene found in this work and those reported in literature.
Thermodynamic models can efficiently be used to calculate vast
amount of phase equilibrium behaviour using limited number of
experimental data.
Abstract: The aim of this study was to compare the solubility of selected volatile organic compounds in water and silicon oil using the simple static headspace method. The experimental design allowed equilibrium achievement within 30 – 60 minutes. Infinite dilution activity coefficients and Henry-s law constants for various organics representing esters, ketones, alkanes, aromatics, cycloalkanes and amines were measured at 303K. The measurements were reproducible with a relative standard deviation and coefficient of variation of 1.3x10-3 and 1.3 respectively. The static determined activity coefficients using shaker flasks were reasonably comparable to those obtained using the gas liquid - chromatographic technique and those predicted using the group contribution methods mainly the UNIFAC. Silicon oil chemically known as polydimethysiloxane was found to be better absorbent for VOCs than water which quickly becomes saturated. For example the infinite dilution mole fraction based activity coefficients of hexane is 0.503 and 277 000 in silicon oil and water respectively. Thus silicon oil gives a superior factor of 550 696. Henry-s law constants and activity coefficients at infinite dilution play a significant role in the design of scrubbers for abatement of volatile organic compounds from contaminated air streams. This paper presents the phase equilibrium of volatile organic compounds in very dilute aqueous and polymeric solutions indicating the movement and fate of chemical in air and solvent. The successful comparison of the results obtained here and those obtained using other methods by the same authors and in literature, means that the results obtained here are reliable.
Abstract: Isobaric vapor-liquid equilibrium measurements are reported for the binary mixtures of Mesitylene + 1-Heptanol and Mesitylene + 1-Octanol at 97.3 kPa. The measurements have been performed using a vapor recirculating type (modified Othmer's) equilibrium still. Both the mixtures show positive deviation from ideality. The Mesitylene + 1-Heptanol mixture forms an azeotrope whereas Mesitylene + 1- Octanol form a non – azeotropic mixture. The activity coefficients have been calculated taking into consideration the vapor phase nonideality. The data satisfy the thermodynamic consistency tests of Herington, and Hirata. The activity coefficients have been satisfactorily correlated by means of the Margules, Redlich-Kister, Wilson, Black, and NRTL equations. The activity coefficient values have also been obtained by UNIFAC method.
Abstract: Isobaric vapor-liquid equilibrium measurements are
reported for binary mixture of 2-Methyltetrahydrofuran and Cumene
at 97.3 kPa. The data were obtained using a vapor recirculating type
(modified Othmer's) equilibrium still. The mixture shows slight
negative deviation from ideality. The system does not form an
azeotrope. The experimental data obtained in this study are
thermodynamically consistent according to the Herington test. The
activity coefficients have been satisfactorily correlated by means of
the Margules, and NRTL equations. Excess Gibbs free energy has
been calculated from the experimental data. The values of activity
coefficients have also been obtained by the UNIFAC group
contribution method.
Abstract: Isobaric vapor-liquid equilibrium measurements are
reported for the binary mixture of Methyl acetate and
Isopropylbenzene at 97.3 kPa. The measurements have been
performed using a vapor recirculating type (modified Othmer's)
equilibrium still. The mixture shows positive deviation from ideality
and does not form an azeotrope. The activity coefficients have been
calculated taking into consideration the vapor phase nonideality. The
data satisfy the thermodynamic consistency tests of Herington and
Black. The activity coefficients have been satisfactorily correlated by
means of the Margules, NRTL, and Black equations. A comparison
of the values of activity coefficients obtained by experimental data
with the UNIFAC model has been made.
Abstract: Group contribution methods such as the UNIFAC are
of major interest to researchers and engineers involved synthesis,
feasibility studies, design and optimization of separation processes as
well as other applications of industrial use. Reliable knowledge of
the phase equilibrium behavior is crucial for the prediction of the fate
of the chemical in the environment and other applications. The
objective of this study was to predict the solubility of selected
volatile organic compounds (VOCs) in glycol polymers and
biodiesel. Measurements can be expensive and time consuming,
hence the need for thermodynamic models. The results obtained in
this study for the infinite dilution activity coefficients compare very
well those published in literature obtained through measurements. It
is suggested that in preliminary design or feasibility studies of
absorption systems for the abatement of volatile organic compounds,
prediction procedures should be implemented while accurate fluid
phase equilibrium data should be obtained from experiment.