Abstract: This study presents three different approaches to
estimate bubble point pressures for the binary system of CO2 and
ethyl palmitate fatty acid ethyl ester. The first method involves the
Peng-Robinson (PR) Equation of State (EoS) with the conventional
mixing rule of Van der Waals. The second approach involves the PR
EOS together with the Wong Sandler (WS) mixing rule, coupled with
the UNIQUAC GE model. In order to model the bubble point
pressures with this approach, the volume and area parameter for ethyl
palmitate were estimated by the Hansen group contribution method.
The last method involved the Peng-Robinson, combined with the
Wong-Sandler method, but using NRTL as the GE model. Results
using the Van der Waals mixing rule clearly indicated that this
method has the largest errors among all three methods, with errors in
the range of 3.96-6.22%. The PR-WS-UNIQUAC method exhibited
small errors, with average absolute deviations between 0.95 to 1.97
percent. The PR-WS-NRTL method led to the least errors, where
average absolute deviations ranged between 0.65-1.7%.
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: 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: Group contribution based models are widely used in
industrial applications for its convenience and flexibility. Although a
number of group contribution models have been proposed, there were
certain limitations inherent to those models. Models based on group
contribution excess Gibbs free energy are limited to low pressures and
models based on equation of state (EOS) cannot properly describe
highly nonideal mixtures including acids without introducing
additional modification such as chemical theory. In the present study
new a new approach derived from quantum chemistry have been used
to calculate necessary EOS group interaction parameters. The
COSMO-RS method, based on quantum mechanics, provides a
reliable tool for fluid phase thermodynamics. Benefits of the group
contribution EOS are the consistent extension to hydrogen-bonded
mixtures and the capability to predict polymer-solvent equilibria up to
high pressures. The authors are confident that with a sufficient
parameter matrix the performance of the lattice EOS can be improved
significantly.
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: This paper is a continuation of our interest in the influence of temperature on specific retention volumes and the resulting infinite dilution activity coefficients. This has a direct effect in the design of absorption and stripping columns for the abatement of volatile organic compounds. The interaction of 13 volatile organic compounds (VOCs) with polydimethylsiloxane (PDMS) at varying temperatures was studied by gas liquid chromatography (GLC). Infinite dilution activity coefficients and specific retention volumes obtained in this study were found to be in agreement with those obtained from static headspace and group contribution methods by the authors as well as literature values for similar systems. Temperature variation also allows for transport calculations for different seasons. The results of this work confirm that PDMS is well suited for the scrubbing of VOCs from waste gas streams. Plots of specific retention volumes against temperature gave linear van-t Hoff plots.
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.