For lithium salts, ionic liquids (ILs) are promising alternatives to conventional solvents in lithium-ion batteries (LIBs) due to a more favorable high-voltage operating window, and due to improved safety through reduction of flammability. Toward better understanding of wetting properties of IL-based electrolytes on a LIB separator, wetting properties affect electrochemical performance, experimental studies were made to determine the influence of solvent, lithium-salt type and salt concentration. Surface tensions and advancing contact angles were measured for two pure ILs ([C(4)C(1)im][BF4] and [C(4)C(1)im][OTf]) and for four IL/alkylcarbonate solvent blends (1:1 mass ratio, [C(4)C(1)im][BF4]/PC, [C(4)C(1)im][BF4]/DMC, [C(4)C(1)im][OTf]/PC, and [C(4)C(1)im][OTf]/ DMC) with several concentrations of a lithium salt (LiClO4, LiPF6, and LiTFSI). A significant improvement of wettability of pure ILs was observed by adding DMC, while adding PC with surface tension higher than that of pure ILs is detrimental to wetting behavior. Contact angles decrease by adding LiTFSI but show almost no change upon addition of LiPF6 or LiClO4. Surface tensions follow the same trend as that for contact angles. Incorporation of TFSI- anion gives favorable separator wettability. Estimates were made for interfacial properties of the separator (dispersive and polar components of the surface free energy for solid-vapor, for liquid-vapor, and for solid-liquid interfacial free energy).

Extraction with nonaqueous solvents provides a straightforward method for the recovery of products from bioconversion reactions. The in situ extraction of products during a bioconversion may be desirable because the products adversely affect the bioconversion, or the environment in the bioreactor adversely affects the products. This chapter presents a summary of extractive fermentations and extractive enzymatic reactions. In many fermentations, accumulation of products in the broth inhibits cell growth or product formation. Whether the products inhibit the growth of the cells or the fermentation environment is deleterious to the products, solvent and broth must be in direct contact so that the products can be extracted into the organic solvent. The largest constraint in selecting an extraction solvent is the requirement that the solvent be biocompatible. Physical properties of the solvent are important during the extraction step of the extractive fermentation process and in later processing steps.

Because of the depletion of fossil fuels and associated environmental problems, the biotechnological production of 1-butanol used as a gasoline blend is of renewed interest. Biobutanol from biomass is obtained in aqueous solution at low concentration with impurities in the fermentation broth. To perform extraction of biobutanol from the aqueous solution, liquid-liquid (LLE) and vapor-liquid equilibria (VLE) are necessary. With this aim, we determined VLE of two pure compounds (1-butanol and 1,3,5-trimethylbenzene) and two binary systems (n-dodecane + 1-butanol and 1,3,5-trimethylbenzene + 1-butanol) as well as carried out LLE measurements at atmospheric pressure of water + butanol (2, 4, and 6% weight in water) + 1,3,5-trimethylbenzene and water + butanol (6% weight in water) + dodecane and the system (1,3,5-trimethylbenzene + water) at 283.15, 303.15, and 333.15 K. Comparison of the two extraction solvents (1,3,5-trimethylbenzene and n-dodecane) shows that the content of butanol in the aqueous phase is very close and the mole fraction for butanol is twice higher in 1,3,5-trimethylbenzene than in n-dodecane. VLE and LLE results were compared with the literature data, a good agreement is observed in both cases. The non-random two liquid (NRTL) model was used for predicting the ternary systems. The adjustable parameters of the model were determined by regression of the binary data (VLE and LLE). Experimental and predicted mutual solubility values are in good agreement.

Empowered by developments in statistical mechanics and information science, molecular thermodynamics continues to play a pivotal role in engineering design of chemical products and industrial processes by providing better understanding and more reliable prediction of the physicochemical properties and phase behavior of chemical systems.

Following Forest Hills High School in New York City, I attended Cornell University for a five-year program leading to a Bachelor of Chemical Engineering degree. After spending one year at the University of Rochester to obtain a Master of Science in Chemical Engineering, I came to Princeton University in 1951. Four years later, with a fresh PhD, I joined the faculty at the University of California, Berkeley, where I remained, interrupted only by sabbatical leaves in Switzerland, Germany, England, New Zealand, and Australia. Most of my professional work has been in applied chemical thermodynamics for process design, in particular, development of molecular-thermodynamic models for calculating phase equilibria for large-scale separation operations. I have also worked on the properties of electrolytes and hydrates, critical phenomena in fluid mixtures, properties of polymers and gels, adsorption of fluid mixtures, and separation of biomolecules. For many years I was a consultant for Air Projects and Chemicals and for the Fluor Corporation. Throughout my long teaching career, I have stressed the importance of context and of integrating science and engineering with humanities and with the needs of society. Such integration makes better engineers and contributes to personal happiness.

On the basis of work by Bernard and Blum [Bernard, O.; Blum, L. Binding Mean Spherical Approximation for Pairing Ions: An Exponential Approximation and Thermodynamics. J. Chem. Phys. 1996, 104, 4746-4754], Barthel et al. [Barthel, J.; Krienke, H.; Holovko, M.; Kapko, V.; Protsykevich, I. The Application of the Associative Mean Spherical Approximation in the Theory of Nonaqueous Electrolyte Solutions. Condens. Matter Phys. 2000, 3, 23], and Simonin et al. [Simonin, J.-P.; Bernard, O.; Blum, L. Real Ionic Solutions in the Mean Spherical Approximation. 3. Osmotic and Activity Coefficients for Associating Electrolytes in the Primitive Model. J. Phys. Chem. B 1998, 102, 4411-4417], this work presents and validates a molecular- thermodynamic model for lithium salt activity coefficients in aqueous and nonaqueous single- and mixed-solvent systems. The Binding Mean Spherical Approximation gives electrolyte activity due to long-range electrostatic forces, short-range hard- sphere repulsion, and ion-pair formation. The theory shows good agreement with measured salt activities up to 3 molar in aqueous and nonaqueous solvents using a solvent-dependent, concentration-independent, center-to-center distance of closest approach between ions as the single fitting parameter for each electrolyte system. For mixed-solvent electrolytes, the local solvation environment around the ions dictates short-range interactions. To account for preferential ion solvation in a mixed solvent, the center-to-center distance is obtained from Wang and co-workers' Dipolar Self-Consistent-Field Theory [Nakamura, I.; Shi, A.-C.; Wang, Z.-G. Ion Solvation in Liquid Mixtures: Effects of Solvent Reorganization. Phys. Rev. Lett. 2012, 109, 257802]. For a particular salt in a binary solvent mixture at fixed temperature, the model predicts salt activity coefficients using only the fitted single-solvent distances-of-closest approach.

Release of crude oil from reservoir rock by low-salinity waterflooding is thought to occur by decreasing the advancing crude oil/brine/rock water contact angle to depin three-phase contact lines (i.e., by increasing reservoir water wettability). Crude oil likely adheres locally to reservoir rock asperities by deposition of asphaltene agglomerates formed at the crude oil/brine interface, following collapse of protective water films. One mechanism proposed for asphaltene adhesion and subsequent release is ion bridging of asphaltenic carboxylate groups protruding through molecularly thin water layers to calcium-occupied rock surface exchange sites, the so-called multicomponent ion exchange mechanism. To our knowledge, however, no experimental evidence directly establishes divalent cation bridging of aqueous carboxylates to anionic mineral surfaces. Using a quartz crystal microbalance with dissipation, we measure adsorption of aqueous carboxylates (benzoate, pentanoate, and hexanoate) onto silica, with and without calcium ion present at near-neutral pH. We find little to no adsorption on a silica surface to within the detection limit of our measurement (+/- 1 Hz, 0.18 mg/m(2)). Modeling of the silica surface chemistry, using classical ion-complexing triple-layer formalism, reveals that less than 10% of surface-hydroxylated sites actually ionize at pH 7. Of these, not all bind calcium ions. Accordingly, the calcium ion surface density is insufficient to reverse the negative surface charge of silica or to promote significant ion bridging of aqueous carboxylates. In so far as aqueous-soluble carboxylic acids mimic those incorporated in crude oil asphaltenes, we conclude that calcium ion bridging alone does not adhere asphaltenes to silica surfaces.

The thermodynamic properties of a working-fluid pair, composed of a refrigerant and an absorbent, greatly influence the performance of an absorption–refrigeration cycle. Particularly important is the solubility of the vaporized refrigerant in the absorbent. Using an isochoric saturation method, solubilities were measured for trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) in 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF6]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim][PF6]), and 1-methyl-3-octylimidazolium hexafluorophosphate ([Omim][PF6]) from 283.15 to 343.15 K. Solubilities rise with a decrease in temperature and an increase in pressure. The highest solubility is in [Omim][PF6], followed by [Hmim][PF6], and [Bmim][PF6]. The new data were correlated by the nonrandom two-liquid model and by the Krichevsky–Ilinskays equation; both provide good agreement with the experimental data. Estimates were given for total enthalpy, entropy, and Gibbs energy of dissolution.

Asphaltenes in crude oil play a pivotal role in reservoir oil production because they control rock-surface wettability. Upon crude oil invasion into a brine-filled reservoir trap, rock adherence of sticky asphaltene agglomerates formed at the crude oil/brine interface can change the initially water-wet porous medium into mixed-oil wetting. If thick, stable water films coat the rock surfaces, however, asphaltenic-oil adhesion is thought to be prevented. We investigate whether water films influence the uptake of asphaltenes in crude oil onto silica surfaces. Water films of known thickness are formed at a silica surface in a quartz crystal microbalance with dissipation and contacted by toluene-solubilized asphaltene. We confirm that thick water films prevent asphaltene molecular contact with the silica surface blocking asphaltene adhesion. The thicker the water film, the smaller is the amount of asphaltene deposited. Film thickness necessary for complete blockage onto silica is greater than about 500 nm, well beyond the range of molecular-chain contact. Water films of thickness less than 500 nm, sandwiched between toluene and solid silica, apparently rupture into thick water pockets and interposed molecularly thin water layers that permit asphaltene adherence.

To obtain osmotic coefficients, a classic static-view apparatus was used to measure the difference between the vapor pressure of a solvent and that of its salt solution at 25 degrees C. Vapor-pressure lowering was measured for solutions containing a lithium salt (LiCI, LiBr, LiNO3, LiPF6 and LITFSI) dissolved in a non-aqueous solvent (dimethyl carbonate, dimethyl sulfoxide and acetonitrile) that may be used in a lithium-ion battery. The osmotic-coefficient data are represented by Archer's extended Pitzer equation. Mean ionic activity coefficients for the salts are calculated from the osmotic-coefficient data. (C) 2018 Elsevier Ltd.

Solubilities were measured for five lithium salts (LiF, LiCl, LiBr, LiPF6, and LiTFSI) in 1-butyl-3-methylimidazolium dicyanamide ([BMIM][N(CN)(2)]) and in 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) from 298.15 to 343.15 K under atmospheric pressure. Measurements were made using inductively coupled plasma-optical emission spectroscopy (ICP-OES). Solubilities increase with rising temperature. The highest solubility is for LiPF6, followed by LiTFSI, LiBr, LiCI, and LiF. In both ionic liquids, LiF is essentially insoluble. A comparison of the solubilities of the same salts in different [BMIM]-based ILs shows that the solubility order is [BMIM][0Tf] < [BMIM] [BF4]< [BMIM] [N(CN)(2)]. The new data were correlated by the Margules equation where the standard state for the salt's activity coefficient is the hypothetical pure liquid salt. Estimates are given for total enthalpy, entropy, and Gibbs energy of dissolution.

Hypothesis: The wetting behavior of an electrolyte solution on the separator, determined by contact angle measurements, has a significant effect on the internal resistance of the battery and on its cycle life. The solvent, the lithium-salt type and its concentration may affect the wettability. However, few systematic studies address the effect of salt concentration on surface tension and contact angle. Experiments: Surface tensions and advancing contact angles were measured for dimethyl sulfoxide (DMSO), propylene carbonate (PC), dimethyl carbonate (DMC), and a PC/DMC mixture (1:1 mass ratio) with various concentrations of a lithium salt (LiCIO4, LiPF6, and LiTFSI) at 23 degrees C. Measurements were made by a Kriiss Drop Shape Analyzer 100, with a video camera mounted on a microscope to record the drop image. Findings: For DMSO, PC and PC/DMC, surface tensions increase by adding LiClO4 or LiPF6 but decrease upon addition of LiTFSI. For DMC, the lithium salts have little impact on the surface tensions. For each solvent, contact angles and adhesion energies follow the same trend as those for surface tensions. The TFSI- anion reduces the surface tension of the solvent, favoring good wettability of the separator. The optimal surface tension for wettability of Celgard 2500 is at or below 26.1 mN/m. (C) 2018 Elsevier Inc. All rights reserved.

Solubilities were measured from 25 to 45 degrees C for six lithium salts (LiF, LiCl, LiBr, LiNO3, LiTFSI and LiPF6) in five pure non-aqueous solvents (ethanol, acetonitrile, dimethyl carbonate, dimethyl sulfoxide and propylene carbonate) and in a few of their binary mixtures (ethanol + DMSO, DMC + DMSO and DMC + PC). The experimental method uses a Varian inductively-coupled plasma-optical-emission spectrometer (ICP-OES). Solubilities increase with rising temperature. At a given temperature, LiNO3 shows the highest solubility in all solvents. Salt solubilities follow the order LiNO3> LiTFSI > LiBr > LiCI > LiPF6 > LiF. The dissolving abilities of the solvents are in the order ethanol > DMSO > acetonitrile > PC > DMC. Coupled with the salt's melting temperature and enthalpy of fusion, liquid-phase activity coefficients for salts were obtained from the solubility data. (C) 2018 Elsevier B.V. All rights reserved.

The properties of working pairs of refrigerant and absorbent have a great influence on the performance of absorption refrigeration cycle. In this work, the measurements of absorption properties for 2,3,3,3-tetrafluoroprop-1-ene/1 -ethy1-3-methylimidazolium tetrafluoroborate ((EMIM)[EF4]), 2,3,3,3-tetrafluoroprop-1-ene/1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][EF4], and 2,3,3,3-tetrafluoroprop-1-ene/1 -methy1-3-octylimidazoliumtetrafluoroborate ([OMIM][BF4]]) between 283.15 and 343.15 K were performed by means of an isochoric saturation method. Experimental data were correlated using NRTL model and Krichevslcy-Kasarnovsky (K-K) equation. The studied results show that absorption of gaseous 2,3,3,3-tetrafluoroprop-1-ene increases with a decrease in temperature and an increase in pressure, and absorption diminished in the following order: [OMIM][BE4] > [HMIM] [BF4] > [EMIM][EF4]. (C) 2017 Elsevier B.V. All rights reserved.

A group-contribution method based on scaled-particle theory was developed to predict Henry's constants for six families of persistent organic pollutants: polychlorinated benzenes, polychlorinated biphenyls, polychlorinated dibenzodioxins, polychlorinated dibenzofurans, polychlorinated naphthalenes, and polybrominated diphenyl ethers. The group-contribution model uses limited experimental data to obtain group-interaction parameters for an easy-to-use method to predict Henry's constants for systems where reliable experimental data are scarce. By using group-interaction parameters obtained from data reduction, scaled-particle theory gives the partial molar Gibbs energy of dissolution, Δg̅2, allowing calculation of Henry's constant, H2, for more than 700 organic pollutants. The average deviation between predicted values of log H2 and experiment is 4%. Application of an approximate van't Hoff equation gives the temperature dependence of Henry's constants for polychlorinated biphenyls, polychlorinated naphthalenes, and polybrominated diphenyl ethers in the environmentally relevant range 0-40 °C.

Solubilities of six lithium salts were measured at 25°C in three imidazolium-based ionic liquids: 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][Tf]) and 1-Butyl-3-methylimidazolium dicyanamide ([BMIM][DCA]). The lithium salts were LiTFSI, LiNO3, LiI, LiTf, LiPF6 and LiBF4. There were large differences in solubility of lithium salts depending on the anion of the salt and on the ionic liquid. The largest difference in solubility was observed for LiNO3. 7Li NMR spectra of the concentrated salt-containing ionic liquids indicate that Li+ and NO3− are strongly associated in the investigated ionic liquids. The different abilities of the ionic liquids to solubilize these associated salts could explain the solubility differences. The ionic conductivity of each salt-containing ionic liquid was measured in the temperature range 15 to 60°C up to concentrations close to the solubility limit at 25°C. The ionic conductivity of the salt-containing ionic liquid decreases with salt concentration. Changing the lithium anion had almost no influence on the conductivity in [BMIM][[DCA] but a noticeable influence on the ionic conductivity in [EMIM][TFSI]. The solubilities in [EMIM][Tf] were too small to detect the effect of the anion of the lithium salt on conductivity.