An association and Wilson activity coefficient model for solubilities of aromatic solid pollutants in supercritical carbon dioxide

The solubilities of various solid pollutants in supercritical carbon dioxide were investigated. The intermolecular interactions play a significant role in determining the solubilities of solids in supercritical carbon dioxide. A new model equation was derived by using the concepts of association and activity coefficient model to correlate the solubilities of solids. The model equation combines the association and Wilson activity coefficient models and includes the interaction potentials between the molecules, which are useful in understanding the behavior of the solid solutes in SCCO2. The new model equation involves five adjustable parameters to correlate the solubilities of solids by incorporating the interactions between the molecules. The equation correlated 75 solid systems with an average AARD of around 9%, which was better than the correlations obtained from standard models such as Mendez Santiago-Teja (MT) model and association model. (C) 2012 Elsevier B.V. All rights reserved.

Experimental determination and activity coefficient based models for mixture solubilities of nitrophenol isomers in supercritical carbon dioxide

The experimental solubilities of the mixture of nitrophenol (m- and p-) isomers were determined at 308, 318 and 328 K over a pressure range of 10-17.55 MPa. Compared to the binary solubilities, the ternary solubilities of m-nitrophenol increased at 308, 318 and 328 K. The ternary solubilities of p-nitrophenol increased at 308 K, while the ternary solubilities decreased at lower pressures and increased at higher pressure at 318 and 328 K. The solubilities of the solid mixtures in supercritical carbon dioxide (SCCO2) were correlated with solution models by incorporating the non-idealities using activity coefficient based models. The Wilson and NRTL activity coefficient models were applied to determine the nature of the interactions between the molecules. The equation developed by using the NRTL model has three parameters and correlates mixture solubilities of solid solutes in terms of temperature and cosolute composition. The equation derived from the Wilson model contains five parameters and correlates solubilities in terms of temperature, density and cosolute composition. These two new equations developed in this work were used to correlate the solubilities of 25 binary solid mixtures including the current data. The average AARDs of the model equations derived using the NRTL and Wilson models for the solid mixtures were found to be 7% and 4%, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Experimental solubilities of two lipid derivatives in supercritical carbon dioxide and new correlations based on activity coefficient models

The solubilities of two lipid derivatives, geranyl butyrate and 10-undecen-1-ol, in SCCO2 (supercritical carbon dioxide) were measured at different operating conditions of temperature (308.15 to 333.15 K) and pressure (10 to 18 MPa). The solubilities (in mole fraction) ranged from 2.1 x 10(-3) to 23.2 x 10(-3) for geranyl butyrate and 2.2 x 10(-3) to 25.0 x 10(-3) for 10-undecen-1-ol, respectively. The solubility data showed a retrograde behavior in the pressure and temperature range investigated. Various combinations of association and solution theory along with different activity coefficient models were developed. The experimental data for the solubilities of 21 liquid solutes along with geranyl butyrate and 10-undecen-1-ol were correlated using both the newly derived models and the existing models. The average deviation of the correlation of the new models was below 15%.

Temperature effects on the activity coefficient of the bicarbonate ion

Natural waters may be chemically studied as mixed electrolyte solutions. Some important equilibrium properties of natural waters are intimately related to the activity-concentration ratios (i.e., activity coefficients) of the ions in solution. An Ion Interaction Model, which is based on Pitzer's (1973) thermodynamic model, is proposed in this dissertation. The proposed model is capable of describing the activity coefficient of ions in mixed electrolyte solutions. The effects of temperature on the equilibrium conditions of natural waters and on the activity coefficients of the ions in solution, may be predicted by means of the Ion Interaction Model presented in this work.

The bicarbonate ion, HCO₃^-, is commonly found in natural waters. This anion plays an important role in the chemical and thermodynamic properties of water bodies. Such properties are usually directly related to the activity coefficient of HCO₃^- in solution. The Ion Interaction Model, as proposed in this dissertation, is used to describe indirectly measured activity coefficients of HCO₃^- in mixed electrolyte solutions.

Experimental pH measurements of MCl-MHCO₃ and MCl-H₂CO₃ solutions at 25°C (where M = K⁺, Na⁺, NH₄⁺, Ca²⁺ or Mg²⁺) are used in this dissertation to evaluate indirectly the MHCO₃ virial coefficients. Such coefficients permit the prediction of the activity coefficient of HCO₃^- in mixed electrolyte solutions. The Ion Interaction Model is found to be an accurate method for predicting the activity coefficient of HCO₃^- within the experimental ionic strengths (0.2 to 3.0 m). The virial coefficients of KHCO₃ and NaHCO₃ and their respective temperature variations are obtained from similar experimental measurements at 10° and 40°C. The temperature effects on the NH₄HCO₃, Ca(HCO₃)₂, and Mg(HCO₃)₂ virial coefficients are estimated based on these results and the temperature variations of the virial coefficients of 40 other electrolytes.

Finally, the Ion Interaction Model is utilized to solve various problems of water chemistry where bicarbonate is present in solution.

Evaluation of the conductor-like screening model for real solvents for the prediction of the water activity coefficient at infinite dilution in ionic liquids

Ionic liquids (ILs) have attracted great attention, from both industry and academia, as alternative fluids for very different types of applications. The large number of cations and anions allow a wide range of physical and chemical characteristics to be designed. However, the exhaustive measurement of all these systems is impractical, thus requiring the use of a predictive model for their study. In this work, the predictive capability of the conductor-like screening model for real solvents (COSMO-RS), a model based on unimolecular quantum chemistry calculations, was evaluated for the prediction water activity coefficient at infinite dilution, gamma(infinity)(w), in several classes of ILs. A critical evaluation of the experimental and predicted data using COSMO-RS was carried out. The global average relative deviation was found to be 27.2%, indicating that the model presents a satisfactory prediction ability to estimate gamma(infinity)(w) in a broad range of ILs. The results also showed that the basicity of the ILs anions plays an important role in their interaction with water, and it considerably determines the enthalpic behavior of the binary mixtures composed by Its and water. Concerning the cation effect, it is possible to state that generally gamma(infinity)(w) increases with the cation size, but it is shown that the cation-anion interaction strength is also important and is strongly correlated to the anion ability to interact with water. The results here reported are relevant in the understanding of ILs-water interactions and the impact of the various structural features of its on the gamma(infinity)(w) as these allow the development of guidelines for the choice of the most suitable lLs with enhanced interaction with water.

Activity of Ferric Oxide in Steelmaking Slag

Refining reactions in steelmaking primarily involve oxidation of impurity element(s). The oxidation potential of the slag and the activity of oxygen in the metal (h(O)) are the major factors controlling these chemical reactions. In turn, the oxidation potential of the slag is influenced strongly by the equilibrium distribution of oxygen between ferrous and ferric oxides. We recently investigated the activity coefficient of FeO in steelmaking slag and the effect of chemical composition thereon. This work is focused on estimation of theactivity coefficient of Fe2O3.

Solubility and activity of oxygen in liquid indium and copper indium alloys

The solubility of oxygen in liquid indium in the temperature range 650–820 °C and in liquid copper-indium alloys at 1100 °C in equilibrium with indium sesquioxide has been measured by a phase equilibration technique. The solubility of oxygen in pure indium is given by the relation log(at.% O) = −4726/T + 3.73 (±0.08) Using the recently measured values for the standard free energy of formation of In2O3 and assuming that oxygen obeys Sievert's law up to saturation, the standard free energy of solution of molecular oxygen in liquid indium is calculated as View the MathML sourceΔG°= −51 440 + 8.07 T (±500) cal where the standard state for dissolved oxygen is an infinitely dilute solution in which activity is equal to atomic per cent. The effect of indium additions on the activity coefficient of oxygen dissolved in liquid copper was measured by a solid oxide galvanic cell. The interaction parameter ϵ0In is given by View the MathML source The experimentally determined variation of the activity coefficient of oxygen in dilute solution in Cu-In alloys is in fair agreement with that predicted by a quasichemical model in which each oxygen atom is assumed to be interstitially coordinated to four metal atoms and the nearest neighbour metal atoms are assumed to lose approximately half their metallic cohesive energies.

Solubility and activity of oxygen in liquid nickel in equilibrium with -Al2O3 and NiO.(1+x)Al2O3

The limiting solubility of oxygen in liquid nickel in equilibrium withα-alumina and nickel aluminate has been measured by inert gas fusion analysis of suction samples in the temperature range 1730 to 1975 K. The corresponding oxygen potential has been monitored by a solid electrolyte cell consisting of calcia stabilized zirconia as the electrolyte and Mo + MoO2 as the reference electrode. The results can be summarized by the following equations: log(at. pct O) = \frac - 10,005T + 4.944 ( ±0.015)log(atpctO)=T−10005+4944(0015) % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn DmO2 /4.606RT = log P O2 1/2 = \frac - 13,550T + 4.411 ( ±0.009)O24606RT=logPO212=T−13550+4411(0009) From simultaneous measurements of the potential and concentration of oxygen in melts, not in thermodynamic equilibrium with alumina and aluminate phases, information on the composition dependence of the activity coefficient and the standard free energy of solution of oxygen is obtained. For the reaction, $\frac{1}{2} O_2 \to \underset{\raise0.3em\hbox{$Missing close brace ΔG o = -72,930 - 7.11T (±840) J gr.at.–1 = + 0.216 at. pct OlogfO=T−500+0216atpctO where the standard state for dissolved oxygen is that which makes the value of activity equal to the concentration (in at. pct) in the limit as concentration approaches zero. The oxygen solubility in liquid nickel in equilibrium with solid NiO, evaluated from thermodynamic data, is compared with information reported in the literature. Implications of the results to the deoxidation equilibria of aluminum in nickel are discussed.

Activity of TiO2 in the System ZrO2-TiO2 and Gibbs Energy of Formation of ZrTiO4

The activity of Ti02 in single and two··phase regions of ihe system ZrOrTi02 has heen measured lIsing solid state cells based on yttria··doped tho ria (YDT) as the solid electrolyte at 1373 K. The cells used can be represented as: Pt, Tio.07PtO.Y3 + Zrj.,Tix0 2 / YDT / Ti02 + Tio.07Pto.93, Pt Pt, Tio.07Pto.93 + ZrJ.xTix02 + ZrTi04 / YDT / Ti02+ Tio.07PtO.93, Pt In each cell the composition of Pt-Ti alloy was identical at hoth electrodes. The emf of the cell is therefore directly related to the activity of Ti02 in oxide phase or oxide phase mixture: aTiO~ :;: cxp (-4FE/RT). The activity coefficient of Ti02 in th~ zirconia-rich solid solution with monoclinic structure (CUl2 2" XTi02 2" 0) can be expressed as:In the zirconia-rich solid solution with tetragonal structure (0.085 2" X ri02 2" 0.03), the activity coefficient is given by:In YTi02 (± 0.012) = 2.354 (1-XTiO? )2 +0.064 The standard Gibbs energy of formation of ZrTi04 is -5650 (± 200) J/mol at 1373 K .

Synergistic effect in the catalytic activity of lipase Rhizomucor miehei immobilized on zeolites for the production of biodiesel

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Widening the gap between measurement and modelling of secondary organic aerosol properties?

The link between measured sub-saturated hygroscopicity and cloud activation potential of secondary organic aerosol particles produced by the chamber photo-oxidation of α-pinene in the presence or absence of ammonium sulphate seed aerosol was investigated using two models of varying complexity. A simple single hygroscopicity parameter model and a more complex model (incorporating surface effects) were used to assess the detail required to predict the cloud condensation nucleus (CCN) activity from the subsaturated water uptake. Sub-saturated water uptake measured by three hygroscopicity tandem differential mobility analyser (HTDMA) instruments was used to determine the water activity for use in the models. The predicted CCN activity was compared to the measured CCN activation potential using a continuous flow CCN counter. Reconciliation using the more complex model formulation with measured cloud activation could be achieved widely different assumed surface tension behavior of the growing droplet; this was entirely determined by the instrument used as the source of water activity data. This unreliable derivation of the water activity as a function of solute concentration from sub-saturated hygroscopicity data indicates a limitation in the use of such data in predicting cloud condensation nucleus behavior of particles with a significant organic fraction. Similarly, the ability of the simpler single parameter model to predict cloud activation behaviour was dependent on the instrument used to measure sub-saturated hygroscopicity and the relative humidity used to provide the model input. However, agreement was observed for inorganic salt solution particles, which were measured by all instruments in agreement with theory. The difference in HTDMA data from validated and extensively used instruments means that it cannot be stated with certainty the detail required to predict the CCN activity from sub-saturated hygroscopicity. In order to narrow the gap between measurements of hygroscopic growth and CCN activity the processes involved must be understood and the instrumentation extensively quality assured. It is impossible to say from the results presented here due to the differences in HTDMA data whether: i) Surface tension suppression occurs ii) Bulk to surface partitioning is important iii) The water activity coefficient changes significantly as a function of the solute concentration.

Experimental and Computational Characterization of Alloy--Spinel--Corundum Equilibrium in the System Fe--Co--Al--O at 1873K

The three-phase equilibrium between alloy, spinel solid solution and alpha -Al sub 2 O sub 3 in the Fe--Co--Al--O system at 1873k was fully characterized as a function of alloy composition using both experimental and computational methods. The equilibrium oxygen content of the liquid alloy was measured by suction sampling and inert gas fusion analysis. The O potential corresponding to the three-phase equilibrium was determined by emf measurements on a solid state galvanic cell incorporating (Y sub 2 O sub 3 )ThO sub 2 as the solid electrolyte and Cr + Cr sub 2 O sub 3 as the reference electrode. The equilibrium composition of the spinel phase formed at the interface between the alloy and alumina crucible was measured by electron probe microanalysis (EPMA). The experimental results were compared with the values computed using a thermodynamic model. The model used values for standard Gibbs energies of formation of pure end-member spinels and Gibbs energies of solution of gaseous O in liquid Fe and cobalt available in the literature. The activity--composition relationship in the spinel solid solution was computed using a cation distribution model. The variation of the activity coefficient of O with alloy composition in the Fe--Co--O system was estimated using both the quasichemical model of Jacob and Alcock and Wagner's model along with the correlations of Chiang and Chang and Kuo and Chang. The computed results of spinel composition and O potential are in excellent agreement with the experimental data. Graphs. 29 ref.--AA

Characterization of Alloy-Spinel-Corundum Equilibrium in the System Fe-Ni-Al-O

The three phase equilibrium between alloy, spinel solid solution and α-alumina in the Fe-Ni-Al-O system has been fully characterized at 1823K as a function of alloy composition using both experimental and computational methods. The oxygen potential was measured using a solid state cell incorporating yttria-doped thoria as the electrolyte and Cr+ Cr2O3 as the reference electrode. Oxygen concentration of the alloy was determined by an inert gas fusion technique. The composition of the spinel solid solution, formed at the interface between the alloy and an alumina crucible, was determined by EPMA. The variation of the oxygen concentration and potential and composition of the spinel solid solution with mole fraction of nickel in the alloy have been computed using activities in binary Fe-Ni system, free energies of formation of end member spinels FeO•(1+x)Al2O3 and NiO•(1+x)Al2O3 and free energies of solution of oxygen in liquid iron and nickel, available in the literature. Activities in the spinel solid solution were computed using a cation distribution model. The variation of the activity coefficient of oxygen with alloy composition in Fe-Ni-O system was calculated using both the quasichemical model of Jacob and Alcock and the Wagner's model, with the correlation of Chiang and Chang. The computed results for the oxygen potential and the composition of the spinel solid solution are in good agreement with the measurements. The measured oxygen concentration lies between the values computed using models of Wagner and Jacob and Alcock. The results of the study indicate that the deoxidation hyper-surface in multicomponent systems can be computed with useful accuracy using data for end member systems and thermodynamic models.