Solubility In Toluene Research Articles

Spinnable Mesophase Pitch Prepared via Co-carbonization of Fluid Catalytic Cracking Decant Oil and Synthetic Naphthalene Pitch

Using, as starting materials, fluid catalytic cracking decant oil (FDO), rich in short-chain alkyl groups, and synthetic naphthalene pitch (NP), with stable naphthenic structures, the synthesis of a spinnable mesophase pitch via a co-carbonization process was investigated. The effects of NP addition and the precursor molecular structure on properties of the resultant mesophase pitches and their carbon fiber derivatives were also discussed. With the increase of NP inclusion from 10wt% to 30wt%, the solubility in Toluene and Quinoline and the optically anisotropic domain size of the synthesized pitches increase. However, the softening points of the resultant mesophase pitches decrease. In comparison with FDO, more naphthenic structures are retained in NP and these show higher thermal stability during the preparation of mesophase pitch. The interaction of naphthenic structures in NP and short-chain alkyl groups in FDO promotes an increase in the molecular weight of the mesophase pitch prepared via co-carbonization and, in the present case, also increases the orientation and domain size in the resulting mesophase liquid crystal. The synthesized mesophase possesses low softening point, good solubility and 100 vol% mesophase content. Carbon fibers prepared from the co-carbonized mesophase pitch exhibit higher thermal conductivity than that of K-1100.

Toward Predictive Molecular Dynamics Simulations of Asphaltenes in Toluene and Heptane.

The conventional definition of asphaltenes is based on their solubility in toluene and their insolubility in heptane. We have utilized this definition to study the influence of partial charge parametrization on the aggregation behavior of asphaltenes using classical atomistic molecular dynamics simulations performed on the microsecond time scale. Under consideration here are toluene- and heptane-based systems with different partial charges parametrized using the general AMBER force field (GAFF). Systems with standard GAFF partial charges calculated by the AM1-BCC and HF/6-31G*(RESP) methods were simulated alongside systems without partial charges. The partial charges implemented differ in terms of the resulting electrical negativity of the asphaltene polyaromatic core, with the AM1-BCC method giving the greatest magnitude of the total core charge. Based on our analysis of the molecular relaxation and orientation, and on the aggregation behavior of asphaltenes in toluene and heptane, we proposed to use the partial charges obtained by the AM1-BCC method for the study of asphaltene aggregates. A good agreement with available experimental data was observed on the sizes of the aggregates, their fractal dimensions, and the solvent entrainment for the model asphaltenes in toluene and heptane. From the results obtained, we conclude that for a better predictive ability, simulation parameters must be carefully chosen, with particular attention paid to the partial charges owing to their influence on the electrical negativity of the asphaltene core and on the asphaltenes aggregation.

Toluene permeation through solid polymer electrolyte during toluene direct electro-hydrogenation for energy carrier synthesis

For the transportation and storage of hydrogen energy by toluene-methylcyclohexane organic hydride systems, the performance of toluene direct electro-hydrogenation electrolyzers using solid polymer electrolytes (SPE) for the membrane and ionomers must be improved. In this study, we investigate the effect of the equivalent weight (EW) and the side-chain length of the SPE on toluene permeability and electrochemical performance. The SPE membrane with a lower EW and a shorter side chain shows a lower toluene permeability. The lower EW, with higher acidity, decreases toluene solubility by salting-out in the hydrophilic mass transport path. The shorter side chain, which lowers the water uptake, suppresses toluene permeation by decreasing the cross-sectional area of the mass transport path. In the electrochemical measurement using the electrolyzer, the combination of SPEs with long side chain and high EW for both the membrane and ionomer shows the best performance. For long-term anode deactivation by membrane-permeated toluene, the membrane should be designed to reduce toluene permeability. Meanwhile, the ionomer has the advantage of higher EW and long side chain.

Solubility measurements and thermodynamic modeling of pyrazinamide in five different solvent-antisolvent mixtures

Pyrazinamide, an important first line drug for the treatment of Mycobacterium tuberculosis, has different polymorphic forms among which the plate like metastable δ-polymorphic form is desirable for ease of downstream processing. Pyrazinamide has reasonably good solubility in acetone, 1,4-dioxane and methanol; but very low solubility in toluene and cyclohexane. Also, the δ-polymorphic form of pyrazinamide can be obtained by antisolvent crystallization using any of these five solvent-antisolvent pairs. In this work, the solubility of pyrazinamide in acetone-toluene, acetone-cyclohexane, 1,4-dioxane-toluene, 1,4-dioxane-cyclohexane and methanol-toluene mixtures is measured by gravimetric method within the temperature range of 283.15 K to 333.15 K over antisolvent composition upto 70 wt%. The solubility of pyrazinamide increases with increase in temperature for all systems at constant antisolvent (toluene and cyclohexane) composition and decreases with increase in antisolvent composition for the given temperature range for all systems except methanol-toluene system. The solubility of pyrazinamide in methanol-toluene system increases with increase in toluene composition upto 40 wt% and then decreases with increase in toluene composition. Three thermodynamic models namely UNIQUAC, NRTL, and Wilson are used to correlate the solubility of pyrazinamide in above solvent-antisolvent mixtures. A nonlinear optimization technique was used to determine the adjustable parameters of various models. The accuracy of the model correlation has been evaluated on the basis of relative average deviation, root mean square deviation and Akaike Information Criterion. All the models represented the experimental solubility data with good accuracy, the maximum root mean square deviation being 5.21. The dissolution enthalpy and dissolution entropy of pyrazinamide in above solution mixtures were calculated from the slope and intercept of van't Hoff equation which shows that solvation of pyrazinamide in these mixed solvents is endothermic and enthalpy-driven.

Effect of the oxygen content and the functionality of spinnable pitches derived from ethylene tar by distillation on the mechanical properties of carbon fibers

Three basic pitches were prepared by the distillation of ethylene tar at 200, 250, or 300 °C for 3 h. Spinnable pitches were produced from them using air-blowing followed by heat treatment at 330°C for 4 h and are designated P200AT, P250AT and P300AT, respectively. These three pitches, and stabilized fibers and carbon fibers produced from them were characterized by TG-MS, FT-IR, 13C-NMR, XRD, SEM, solubility tests and elemental analysis. The components and oxidation reactivity of the basic pitches, and its influence on the oxygen functionality and microstructures of the spinnable pitches and mechanical properties of the resulting carbon fibers were investigated. Results showed that with increasing distillation temperature the aliphatic carbon content and n-hexane and toluene solubility of the basic pitches decreased, while their aromaticity and planarity increased, and the oxidation reactivity reached a maximum at 250 °C. Of the three spinnable pitches P250AT had the highest softening point, highest carbon yield, oxygen content, and C=O content and the highest toluene insoluble fraction. However, the oxygen uptake of P250AT pitch fibers during stabilization was the lowest among the three. This led to a reduction of gas release during carbonization, and therefore the highest carbon yield, the smallest number of defects, the highest tensile strength and the lowest Young's modulus of all the carbon fibers.

Insight into the oxidative reactivity of pitch fractions for predicting and optimizing the oxidation stabilization of pitch

Oxidative stability is of particular importance to maintain the morphology and adjust physicochemical properties of pitch-based carbon products. Due to the complex composition of pitch, the oxidative reactivity of the pitch components has rarely been reported to date, so that the oxidative stabilization conditions of pitch have been mainly selected from experience. In the study, a coal tar pitch was fractionated into toluene-soluble (TS), toluene-insoluble and pyridine-soluble (PS), pyridine-insoluble and quinoline-soluble (QS), and quinoline-insoluble (QI) fractions. The molecular structural features of each fraction and their reactivity with oxygen at varying oxidation temperature were characterized and evaluated. The results reveal that light fractions (TS and PS) with more alkyl side chains exhibit a higher reactivity at the low oxidation temperature range from 200 to 250 °C, leading to the formation of more cross-linked structures. Meanwhile heavy fractions (QS and QI), with relatively rich isolated aromatic hydrogen, seem to be remarkable in O2 uptake and the formation of C–O structures until the oxidation temperature rises above 250 °C. Insight into group composition of the pitch allows predicting its oxidative stability characteristics and further allowing it to quickly fine-tune operational conditions for time-effective and energy-saving stabilization.

Sulfur Solubilities in Toluene, o-Xylene, m-Xylene and p-Xylene at Temperatures Ranging from 303.15 K to 363.15 K

Sulfur Solubilities in Toluene, o-Xylene, m-Xylene and p-Xylene at Temperatures Ranging from 303.15 K to 363.15 K

Solubility Modeling, Solute–Solvent Interactions, and Thermodynamic Dissolution Properties of p-Nitrophenylacetonitrile in Sixteen Monosolvents at Temperatures Ranging from 278.15 to 333.15 K

The investigation on p-nitrophenylacetonitrile solubility in ethanol, methanol, isopropanol, n-propanol, acetonitrile, acetone, ethyl acetate, toluene, n-butanol, cyclohexane, 2-butanone, isobutanol, acetic acid, 1,4-dioxane, water, and ethylbenzene was performed via the shake-flask technique covering the temperature range from 278.15 to 333.15 K at local atmospheric pressure. The mole fraction solubility of p-nitrophenylacetonitrile increased with an increase of the studied temperature and followed a sequence in the 16 solvents with the exception of 1,4-dioxane: ethyl acetate > acetone > (acetonitrile, 2-butanone) > toluene > acetic acid > ethylbenzene > methanol > ethanol > n-propanol > n-butanol > isopropanol > isobutanol > cyclohexane > water. There was no solvation or polymorphic transformation during the experiment process. Correlation was made for the obtained p-nitrophenylacetonitrile solubility in the 16 solvents using the λh, Apelblat, Wilson, and NRTL models. The obtained maximum relative average deviation was 2.67%, and root-mean-square deviation, 2.57 × 10–3. The solute–solvent and solvent–solvent interactions were studied based on the linear solvation energy relationship approach. Furthermore, the thermodynamic dissolution properties, reduced excess enthalpy, and activity coefficient under infinitesimal condition were also computed.

Separation of toluene from gas phase using supported imidazolium ionic liquid membrane

Investigation on utilization of supported ionic liquids membranes for hydrocarbon separation from the gas phase was performed. Properties of membrane phase, wettability of supports, swelling effects and solubility of toluene were taken into account. Toluene permeation rates were significantly higher than those of pure nitrogen, the selectivity in a range of 17–341 was satisfying for separation. Despite the increase of viscosity resulting from increasing alkyl chain length of imidazolium bis(trifluoromethylsulfonyl)imide [Tf2N] ionic liquids, permeation of toluene increases due to the higher hydrophobicity and therefore separation is solubility-controlled. However, imidazolium trifluoromethanesulfone [TfO] ionic liquids did not follow the same path. Nevertheless, toluene was successfully separated from N2/toluene gas stream using ionic liquid membranes based on both [Tf2N] and [TfO] yet, in the light of the obtained results and literature data these systems are highly recommended for VOCs separation from gas phase.

Insight into controllability and predictability of pore structures in pitch-based activated carbons

Tailoring porosity of pitch-based activated carbons (PACs) on a large scale is of high importance and usually achieved by introducing additives or templates and adjusting activation conditions. Since pitch is a kind of extraordinarily complex mixtures, it is highly necessary to investigate the effect of pitch composition on pore structure of PACs. Herein, a coal-tar pitch was subdivided by solvent fractionation into toluene-soluble (TS), pyridine-soluble (PS), quinoline-soluble (QS), and quinoline-insoluble (QI) fractions followed by activation using KOH or steam, respectively, to obtain PACs. It is found that the formation of pores in PACs is significantly dependent on pitch composition and activation methods. The light fractions (TS and PS) are more favorable for pore development in the KOH-activated carbons, whereas pores in the H2O-activated carbons are easily achieved by using the heavy fractions (QS and QI). The possible pore-formation mechanisms were also proposed, which indicates that the big differences intrinsically originate from the chemical properties (such as molecular size, structures, reactivity with activation agents and rheological behaviors of the molecular aggregations) of pitch compositions. When commercial pitches are employed for the precursors, a synergistic effect on pore development occurs both in KOH- and H2O-activated PACs seriously depending on their mass percentages of light or heavy fractions. It suggests that the mass percentage can be an index to foresee the porous properties of PACs. These findings open up a significantly important and more practical approach applicable to tailor the pores in PACs on an industrial scale just through adjusting pitch compositions.

Contrasting Mechanisms of Spontaneous Adsorption at Liquid-Liquid Interfaces of Nanoparticles Constituted of and Grafted with pH-Responsive Polymers.

Elucidating the mechanisms responsible for spontaneous adsorption of nanoparticles (NPs) at interfaces is important for their application as emulsifiers, bubble stabilizers, or foaming agents. In order to investigate the key factors that control the spontaneous adsorption of NPs at liquid-liquid interfaces, we synthesized seven different types of NPs from pH-responsive polymers poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) and poly(2-dimethylamino)ethyl methacrylate) (PDMAEMA) via surfactant-free emulsion polymerization or via "grafting from" polystyrene (PS) NPs. The dynamic interfacial tension (IFT) measurements at the toluene-water (Tol-H2O) interface reveal that when PDEAEMA and PDMAEMA are grafted from the surface of PS NPs the solubility of the grafted pH-responsive polymers in toluene is the key factor determining the NPs' interfacial adsorption. Under acidic conditions (pH < 6.0), PDEAEMA and PDMAEMA are protonated and show no solubility in toluene, and as a result, the grafted NPs do not adsorb at the Tol-H2O interface. Oppositely, under basic conditions (pH > 7.0), PDMAEMA dissolves in toluene and therefore the PDMAEMA-grafted NPs can adsorb at the Tol-H2O interface. Interestingly, when NPs are constituted of PDEAEMA, they can adsorb spontaneously at the Tol-H2O interface under acidic conditions (pH < 6.0) but not under basic conditions (pH > 7.0). In this case, the key factor determining the NPs' spontaneous adsorption at the Tol-H2O interface is the degree of softness of the NPs rather than the solubility of PDEAEMA in toluene. Furthermore, we found that the adsorption of NPs constituted of PDEAEMA- (pH 2.0-6.0) and PDMAEMA-grafted PS NPs (pH 7.0-10.0) at the Tol-H2O interface is a combination of diffusion-controlled and energy-barrier-controlled. The opposite trends observed for the interfacial attachment Δ E and activation energies Ea for the "constituted of" and "grafted from" NPs with pH suggest an opposite mechanisms of adsorption at the Tol-H2O interface. Finally, the synthesized NPs prove to be effective emulsifiers, where the phase of the Pickering emulsions can be changed dynamically by pH adjustment.

A Novel Lubricant Based on Covalent Functionalized Graphene Oxide Quantum Dots

Dodecyl amine edge functionalized few-layer graphene oxide quantum dots were synthesized in good yields. The covalent functionalization was demonstrated with NMR and AFM-IR. The resulting structure and particle size was measured with AFM and HRTEM. The thermal stability of the compound was investigated and showed a stability of up to 220 °C. The modified graphene oxide quantum dots showed excellent solubility in various organic solvents, including ethers, methanol, toluene, n-hexane, heptane, xylene, dichloromethane and toluene. The stability of a resulting toluene solution was also proven by static light scattering measurements over several days. The excellent solubility gives the possibility of an efficient and fast spray application of the functionalized graphene oxide quantum dots to steel surfaces. Hence, the macroscopic friction behavior was investigated with a Thwing-Albert FP-2250 friction tester. A thin film of the dodecyl amine functionalized graphene oxide quantum dots on steel lowered the friction coefficient from 0.17 to 0.11 and revealed a significant corrosion inhibition effect.

Development of technology for the alkylation of hydroquinone with aliphatic alcohols

The paper presents the results of research of technology of alkylation of hydroquinone, propyl, isopropyl, isobutyl and tert-butyl alcohols in the presence of concentrated phosphoric acid. The temperature of the alkylation reaction was maintained between 70–72 °С. On the basis of literature data and preliminary investigations the reaction was performed for 4 hours. Upon completion of the reaction, we removed the unreacted hydroquinone, aliphatic alcohol and phosphoric acid are added to a solution of distilled water (solvent corresponding connections) and sodium bicarbonate to slightly acidic (pH 5–6). For separation from the reaction medium of alkylhydroquinones in the reaction mixture was added benzene in which the original hydroquinone dissolves much less. Concentration of the benzene extract alkylhydroquinones conducted by Stripping the solvent under vacuum at temperatures above 70 °С in air atmosphere. Higher temperature vacuum distillation AIDS in the oxidation of alkylhydroquinones to alkylphenones. Precipitated after crystallization, alkylhydroquinones were dried under vacuum in a drying pistol at 56 °С. Dried products were identified by defining the melting temperature, the study of spectral characteristics and qualitative reactions with FeCl3. We also studied the solubility of alkylhydroquinones in various solvents, which showed low solubility of alkylhydroquinones in water, benzene, toluene and higher solubility in propyl and isopropyl alcohols and in acetone. Analysis of the results shows that the obtained alkylhydroquinones are not chemically pure compounds, and contain in their composition of admixture source of hydroquinone. Qualitative reactions of solutions of alkylhydroquinones with FeCl3 solution differ from the corresponding reaction of a solution of hydroquinone. The results of investigations of electronic absorption spectra of alkylhydroquinones and source of hydroquinone in isopropyl alcohol solution did not significantly differ from each other and have a maximum absorption at ? = 210 nm. From the presented investigations it follows that the maximum efficiency of the alkylation of hydroquinone was studied aliphatic alcohols in acidic medium is observed for t-butyl alcohol.

Synthesis, photophysical, structural and electronic properties of novel regioisomerically pure 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic monoimide dibutylester derivatives

Three new isomerically pure 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic monoimide dibutylester derivatives namely; N-[2-(diethylamino)ethyl]-1,7-dibromoperylene-3,4,9,10-tetracarboxy monoimide dibutylester (PMD-1), N-[2-(diethylamino)ethyl]-1,7-di(4-tert-butylphenoxy)perylene-3,4,9,10-tetracarboxy monoimide dibutylester (PMD-2) and N-[2-(diethylamino)ethyl]-1,7-di(pyrrolidinyl)perylene-3,4,9,10-tetracarboxy monoimide dibutylester (PMD-3), have been synthesized and their electronic absorption spectra, and steady-state fluorescence were investigated experimentally as well as by using density functional theory (DFT) calculations. All three compounds show good solubility in toluene and chloroform. Attachment of two tert-butylphenoxy groups at the 1,7-positions in PMD-2 resulted in a red shifted absorption band with an absorption maximum at 518 nm. UV/Vis absorption spectrum of PMD-3 bearing electron donating pyrrolidinyl groups at the 1,7-positions shows a broad absorption band within the visible region, extending to red region. Absorption maximum of lowest energy transition now shifts to 653 nm. In addition to the S0 → S1 absorption bands, bands belonging to S0 → S2 electronic transitions were observed at 378, 386, and 411 nm for PMD-1, PMD-2, and PMD-3 respectively. Compounds PMD-1, PMD-2 and PMD-3 display low fluorescence quantum yields of 0.027, 0.040 and 0.001, respectively in chloroform. DFT calculations revealed that the attachment of electron donating groups at 1,7-positions of perylene core, results in an increase in frontier orbitals energy levels. Observed energy increase in HOMO level is larger in each case, compared to the energy increase in LUMO levels, due to the higher contribution of side groups to HOMO. DFT calculated band gaps for PMD-1, PMD-2 and PMD-3 are 2.68, 2.63 and 2.29 eV respectively.

Solubility Modeling and Mixing Properties for Benzoin in Different Monosolvents and Solvent Mixtures at the Temperature Range from 273.15 to 313.15 K

In the present work, the benzoin solubility in ethanol, methanol, n-propanol, isopropyl alcohol, n-butanol, acetone, ethyl acetate, acetonitrile, cyclohexane, butyl acetate, isobutyl alcohol, and toluene and ethyl acetate + ethanol solvent mixtures was measured by using the static method at the temperature range from 273.15 to 313.15 K under atmospheric pressure (101.1 kPa). The solubilities in mole fraction increased with increasing temperature and followed the order from high to low in the selected monosolvents: ethyl acetate > acetone > butyl acetate > (acetonitrile, toluene) > methanol > ethanol > n-propanol > n-butanol > isobutyl alcohol > isopropyl alcohol > cyclohexane; and for the ethyl acetate + ethanol mixture, the mole fraction solubilities of benzoin increased with the increase in temperature and ethyl acetate mass fraction. The obtained solubility of benzoin in neat solvents was correlated with the Apelblat equation, λh equation, and Wilson and NRTL models; and in solvent mixtures of ethyl ac...

Organic solvent-resistant and thermally stable polymeric microfiltration membranes based on crosslinked polybenzoxazine for size-selective particle separation and gravity-driven separation on oil-water emulsions

Polymeric membranes, compared with their inorganic counterparts, usually suffer from insufficient solvent resistance and thermal stability. In this study, an organic solvent–resistant thermally stable polymeric microfiltration membrane is prepared with a self-crosslinkable polybenzoxazine as a precursor. The obtained membranes have pore sizes of approximately 3.4µm and superior antiswelling stability in organic solvents; thus, they exhibit excellent performance in terms of size-selective particle separation inorganic phases. The membranes are also effective in the gravity-driven separation of surfactant-stabilized water-in-oil emulsions. The water contents of the filtrate oil phases are close to the natural solubility of water in the solvents; for example, a water content of 350ppm, which is comparable to the water solubility in toluene (330ppm), has been found in the filtrate toluene from water-in-toluene emulsions. Moreover, the membrane demonstrates pH-induced changes in oil and water selectivity in oil–water separations. When treated with a strong base solution, the oil-selective membrane becomes water-selective and exhibits favorable performance in terms of separating organic solvents from surfactant-stabilized oil-in-water emulsions. These features effectively extend the application scope of the prepared membrane for oil–water separations.

Achieving over 9.8% Efficiency in Nonfullerene Polymer Solar Cells by Environmentally Friendly Solvent Processing

Nowadays, most of the solution-processed high-efficiency polymer solar cell (PSC) devices are fabricated by halogenated solvents (such as chlorobenzene, 1,2-dichlorobenzene, chloroform, etc.) which are harmful to people and the environment. Therefore, it is essential to develop high-efficiency PSC devices processed by environmentally friendly solvent processing for their industrialization. In this regard, we report a new alkylthio chain-based conjugated polymer PBDB-TS as donor material for environmentally friendly solvent-processed PSCs. PBDB-TS possesses a low-lying HOMO energy level at -5.42 eV and a good solubility in toluene and o-xylene. By using o-xylene and 1% N-methylpyrrolidone as processing solvent, following by the thermal annealing treatment for PBDB-TS:ITIC blend films, well-developed morphological features, and balanced charge transport properties are observed, leading to a high power conversion efficiency (PCE) of 9.85%, higher than that of the device cast from halogenated solvent (PCE = 9.65%). The results suggest that PBDB-TS is an attractive donor material for nonhalogen solvents-processing PSCs.

A Novel Approach for Measuring Gas Solubility in Liquids Using a Tube‐in‐Tube Membrane Contactor

AbstractA novel approach using a semipermeable Teflon AF‐2400 tube‐in‐tube membrane contactor was developed for the measurement of gas solubility in organic solvents. This membrane ensures gas saturation of liquids in continuous flow at a specific pressure and temperature. After liquid decompression, the amount of gas outgassed was measured with a bubble meter and used for solubility calculation. The proposed method was applied to the measurement of oxygen solubility in toluene and benzyl alcohol. Validation experiments were initially performed by comparing the obtained oxygen solubility in toluene with literature data. With higher temperature, the solubility of oxygen in benzyl alcohol was found to increase, indicating that the oxygen‐dissolving process is endothermic. Finally, an empirical correlation of Henry's law constant as a function of temperature was determined.

Reactions of [rad]Sn(Si(tBu)2Me)3 with HM(CO)3C5R5 (M = Cr or Mo, R = H or CH3) and Hg. Ionic, covalent, and μ-CO bonding patterns between transition metals and tin

Hydrogen atom transfer (HAT) reactions to the planar triorganotin radical Sn(Si(tBu)2Me)3 from HMo(CO)3C5H5 and HCr(CO)3C5R5 (R=H, Me) have been investigated at room temperature in toluene or pentane solution. Sn(Si(tBu)2Me)3 and HMo(CO)3C5H5 react rapidly to yield the previously unreported tin hydride HSn(Si(tBu)2Me)3 and [Sn(Si(tBu)2Me)3]+[Mo(CO)3C5H5]−. Similarly, Sn(Si(tBu)2Me)3 and HCr(CO)3C5H5 react at a slower rate to produce HSn(Si(tBu)2Me)3 and a complex formulated as Cp(CO)2CrCOSn(Si(tBu)2Me)3 based on its solubility in toluene, infrared spectrum, and computational studies. A product with identical spectroscopic properties to the proposed Cp(CO)2CrCOSn(Si(tBu)2Me)3 is obtained rapidly in the reaction of Sn(Si(tBu)2Me)3 and [Cr(CO)3C5H5]2. Reaction of Sn(Si(tBu)2Me)3 and HCr(CO)3C5Me5 does not occur at a significant rate at room temperature nor does reaction of Cr(CO)3C5Me5 and HSn(Si(tBu)2Me)3. Fast exchange between HCr(CO)3C5H5 and [Cr(CO)3C5H5]2 results in a single broad peak in the cyclopentadienyl area for mixtures of these two complexes in toluene-d8 at room temperature implying that Cr–Cr bond cleavage and also hydrogen atom transfer (HAT) are faster than the NMR time scale. Computational studies accurately reflect experimental observations. The computed Sn–H bond dissociation enthalpy (BDE) of only 66.7kcal/mol in HSn(Si(tBu)2Me)3 places it near the values for M-H BDE in HM(CO)3C5H5 (M=Cr, Mo) leading to a near equilibrium situation with respect to HAT. Reaction of Sn(Si(tBu)2Me)3 and elemental Hg forms the linear trinuclear HgSn2 cluster Hg[Sn(Si(tBu)2Me)3]2. The crystal structures of Hg[Sn(Si(tBu)2Me)3]2 and BrSn(Si(tBu)2Me)3 are reported.

Predicting the Solubility of CO2 in Toluene + Ionic Liquid Mixtures with PC-SAFT

Perturbed-chain statistical associating fluid theory (PC-SAFT) was applied for modeling the vapor–liquid equilibrium of CO2 + toluene + ionic liquid (IL) mixtures and the molar volume of their liquid phases at temperatures between 298.15 K and 333.15 K and at pressures up to 80 bar. ILs used for this study contain the bis(trifluoromethylsulfonylimide) anion ([Tf2N]−) and imidazolium, pyridinium, thiolanium, and phosphonium cations. The pure-IL PC-SAFT parameters were fit to pure-IL liquid density data. Temperature-dependent binary interaction parameters were fit to binary liquid–liquid equilibrium data (i.e., toluene + IL) obtained from the literature and some points measured for this work. Temperature independent binary interaction parameters were fit to vapor–liquid equilibrium data (CO2 + IL, CO2 + toluene) from the literature. The availability of the pure-IL parameters and binary interaction parameters allowed prediction of CO2 solubility in toluene + IL mixtures with an absolute average relative devi...