Abstract: An ammonium based ionic liquid (methyltrioctylammonium chloride) [N8 8 8 1] [Cl] was investigated as an extraction potential solvent for volatile organic solvents (in this regard, solutes), which includes alkenes, alkanes, ketones, alkynes, aromatic hydrocarbons, tetrahydrofuran (THF), alcohols, thiophene, water and acetonitrile based on the experimental activity coefficients at infinite THF measurements were conducted by the use of gas-liquid chromatography at four different temperatures (313.15 to 343.15) K. Experimental data of activity coefficients obtained across the examined temperatures were used in order to calculate the physicochemical properties at infinite dilution such as partial molar excess enthalpy, Gibbs free energy and entropy term. Capacity and selectivity data for selected petrochemical extraction problems (heptane/thiophene, heptane/benzene, cyclohaxane/cyclohexene, hexane/toluene, hexane/hexene) were computed from activity coefficients data and compared to the literature values with other ionic liquids. Evaluation of activity coefficients at infinite dilution expands the knowledge and provides a good understanding related to the interactions between the ionic liquid and the investigated compounds.
Abstract: Spent bleaching earth (SBE) recycling and utilization as an adsorbent to eliminate dyes from aqueous solution was studied. Organic solvents and subsequent thermal treatment were carried out to recover and reactivate the SBE. The effect of pH, temperature, dye’s initial concentration, and contact time on the dye removal using recycled spent bleaching earth (RSBE) was investigated. Recycled SBE showed better removal affinity of cationic than anionic dyes. The maximum removal was achieved at pH 2 and 8 for anionic and cationic dyes, respectively. Kinetic data matched with the pseudo second-order model. The adsorption phenomenon governing this process was identified by the Langmuir and Freundlich isotherms for anionic dye while Freundlich model represented the sorption process for cationic dye. The changes of Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were computed and compared through thermodynamic study for both dyes.
Abstract: In this study, malt bagasse, a low-cost waste biomass, was tested as a biosorbent to remove the cationic dye Malachite green (MG) from aqueous solution. Batch biosorption experiments were investigated as functions of different experimental parameters such as initial pH, salt (NaCl) concentration, contact time, temperature and initial dye concentration. Higher removal rates of MG were obtained at pH 8 and 10. The equilibrium and kinetic studies suggest that the biosorption follows Langmuir isotherm and the pseudo-second-order model. The maximum monolayer adsorption capacity was estimated at 117.65 mg/g (at 45 °C). According to Dubinin–Radushkevich (D-R) isotherm model, biosorption of MG onto malt bagasse occurs physically. The thermodynamic parameters such as Gibbs free energy, enthalpy and entropy indicated that the MG biosorption onto malt bagasse is spontaneous and endothermic. The results of the ionic strength effect indicated that the biosorption process under study had a strong tolerance under high salt concentrations. It can be concluded that malt bagasse waste has potential for application as biosorbent for removal of MG from aqueous solution.
Abstract: Environmental contamination is a major problem being faced by the society today. Industrial, agricultural, and domestic wastes, due to the rapid development in the technology, are discharged in the several receivers. Generally, this discharge is directed to the nearest water sources such as rivers, lakes, and seas. While the rates of development and waste production are not likely to diminish, efforts to control and dispose of wastes are appropriately rising. Wastewaters from textile industries represent a serious problem all over the world. They contain different types of synthetic dyes which are known to be a major source of environmental pollution in terms of both the volume of dye discharged and the effluent composition. From an environmental point of view, the removal of synthetic dyes is of great concern. Among several chemical and physical methods, adsorption is a promising technique due to the ease of use and low cost compared to other applications in the process of discoloration, especially if the adsorbent is inexpensive and readily available. The focus of the present study was to assess the potentiality of Brahea edulis (BE) for the removal of synthetic dye Yellow bemacid (YB) from aqueous solutions. The results obtained here may transfer to other dyes with a similar chemical structure. Biosorption studies were carried out under various parameters such as mass adsorbent particle, pH, contact time, initial dye concentration, and temperature. The biosorption kinetic data of the material (BE) was tested by the pseudo first-order and the pseudo-second-order kinetic models. Thermodynamic parameters including the Gibbs free energy ΔG, enthalpy ΔH, and entropy ΔS have revealed that the adsorption of YB on the BE is feasible, spontaneous, and endothermic. The equilibrium data were analyzed by using Langmuir, Freundlich, Elovich, and Temkin isotherm models. The experimental results show that the percentage of biosorption increases with an increase in the biosorbent mass (0.25 g: 12 mg/g; 1.5 g: 47.44 mg/g). The maximum biosorption occurred at around pH value of 2 for the YB. The equilibrium uptake was increased with an increase in the initial dye concentration in solution (Co = 120 mg/l; q = 35.97 mg/g). Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The best fit was obtained by the Langmuir model with high correlation coefficient (R2 > 0.998) and a maximum monolayer adsorption capacity of 35.97 mg/g for YB.
Abstract: Experimental data of refractive index, excess molar volume and viscosity of binary mixture of morpholine with cumene over the whole composition range at 298.15 K, 303.15 K, 308.15 K and normal atmospheric pressure have been measured. The experimental data were used to compute the density, deviation in molar refraction, deviation in viscosity and excess Gibbs free energy of activation as a function of composition. The experimental viscosity data have been correlated with empirical equations like Grunberg- Nissan, Herric correlation and three body McAllister’s equation. The excess thermodynamic properties were fitted to Redlich-Kister polynomial equation. The variation of these properties with composition and temperature of the binary mixtures are discussed in terms of intermolecular interactions.
Abstract: The influence of the crystal field interactions on the mixed spin-3/2 and spin-5/2 ferrimagnetic Ising system is considered by using the mean field theory based on Bogoliubov inequality for the Gibbs free energy. The ground-state phase diagram is constructed, the phase diagrams of the second-order critical temperatures are obtained, and the thermal variation of the sublattice magnetizations is investigated in detail. We find some interesting phenomena for the sublattice magnetizations at particular values of the crystal field interactions.
Abstract: The equilibrium chemical reactions taken place in a converter reactor of the Khorasan Petrochemical Ammonia plant was studied using the minimization of Gibbs free energy method. In the minimization of the Gibbs free energy function the Davidon– Fletcher–Powell (DFP) optimization procedure using the penalty terms in the well-defined objective function was used. It should be noted that in the DFP procedure along with the corresponding penalty terms the Hessian matrices for the composition of constituents in the Converter reactor can be excluded. This, in fact, can be considered as the main advantage of the DFP optimization procedure. Also the effect of temperature and pressure on the equilibrium composition of the constituents was investigated. The results obtained in this work were compared with the data collected from the converter reactor of the Khorasan Petrochemical Ammonia plant. It was concluded that the results obtained from the method used in this work are in good agreement with the industrial data. Notably, the algorithm developed in this work, in spite of its simplicity, takes the advantage of short computation and convergence time.
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: Batch adsorption of recalcitrant melanoidin using the abundantly available coal fly ash was carried out. It had low specific surface area (SBET) of 1.7287 m2/g and pore volume of 0.002245 cm3/g while qualitative evaluation of the predominant phases in it was done by XRD analysis. Colour removal efficiency was found to be dependent on various factors studied. Maximum colour removal was achieved around pH 6, whereas increasing sorbent mass from 10g/L to 200 g/L enhanced colour reduction from 25% to 86% at 298 K. Spontaneity of the process was suggested by negative Gibbs free energy while positive values for enthalpy change showed endothermic nature of the process. Non-linear optimization of error functions resulted in Freundlich and Redlich-Peterson isotherms describing sorption equilibrium data best. The coal fly ash had maximum sorption capacity of 53 mg/g and could thus be used as a low cost adsorbent in melanoidin removal.
Abstract: This paper unifies power optimization approaches in
various energy converters, such as: thermal, solar, chemical, and
electrochemical engines, in particular fuel cells. Thermodynamics
leads to converter-s efficiency and limiting power. Efficiency
equations serve to solve problems of upgrading and downgrading of
resources. While optimization of steady systems applies the
differential calculus and Lagrange multipliers, dynamic optimization
involves variational calculus and dynamic programming. In reacting
systems chemical affinity constitutes a prevailing component of an
overall efficiency, thus the power is analyzed in terms of an active
part of chemical affinity. The main novelty of the present paper in the
energy yield context consists in showing that the generalized heat
flux Q (involving the traditional heat flux q plus the product of
temperature and the sum products of partial entropies and fluxes of
species) plays in complex cases (solar, chemical and electrochemical)
the same role as the traditional heat q in pure heat engines.
The presented methodology is also applied to power limits in fuel
cells as to systems which are electrochemical flow engines propelled
by chemical reactions. The performance of fuel cells is determined by
magnitudes and directions of participating streams and mechanism of
electric current generation. Voltage lowering below the reversible
voltage is a proper measure of cells imperfection. The voltage losses,
called polarization, include the contributions of three main sources:
activation, ohmic and concentration. Examples show power maxima
in fuel cells and prove the relevance of the extension of the thermal
machine theory to chemical and electrochemical systems. The main
novelty of the present paper in the FC context consists in introducing
an effective or reduced Gibbs free energy change between products p
and reactants s which take into account the decrease of voltage and
power caused by the incomplete conversion of the overall reaction.
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: The equilibrium, thermodynamics and kinetics of the
biosorption of Cd (II) and Pb(II) by a Spore Forming Bacillus (MGL
75) were investigated at different experimental conditions. The
Langmuir and Freundlich, and Dubinin-Radushkevich (D-R)
equilibrium adsorption models were applied to describe the
biosorption of the metal ions by MGL 75 biomass. The Langmuir
model fitted the equilibrium data better than the other models.
Maximum adsorption capacities q max for lead (II) and cadmium (II)
were found equal to 158.73mg/g and 91.74 mg/g by Langmuir model.
The values of the mean free energy determined with the D-R equation
showed that adsorption process is a physiosorption process. The
thermodynamic parameters Gibbs free energy (ΔG°), enthalpy (ΔH°),
and entropy (ΔS°) changes were also calculated, and the values
indicated that the biosorption process was exothermic and
spontaneous. Experiment data were also used to study biosorption
kinetics using pseudo-first-order and pseudo-second-order kinetic
models. Kinetic parameters, rate constants, equilibrium sorption
capacities and related correlation coefficients were calculated and
discussed. The results showed that the biosorption processes of both
metal ions followed well pseudo-second-order kinetics.