Yizhak Marcus's research while affiliated with Hebrew University of Jerusalem and other places

Publications (64)

Article
The cohesive energy densities ced and the internal pressures Pint of aqueous acetone mixtures are calculated from literature data for the entire composition range at 298.15 K at saturation pressures. The ratios Pint/ced are measures of the ‘structuredness’ of the studied fluids, the small values noted signify ‘tight’ structures, due to the hydrogen...
Article
The preferential solvation parameters for the self-association and the mutual association of each of N,N-dimethylformamide and propylene carbonate with a co-solvent in their binary mixtures as well as the self-association of each of these components at infinite dilution in the other component as solvent have been calculated from previously reported...
Article
Full-text available
Carbon dioxide as a solute interacts with solvents mainly via dispersion forces. Its Hildebrand solubility parameter, δH, may therefore be used to predict its dissolution. The usual definition of δH, involving ΔvH, the molar enthalpy of vaporization, is inapplicable for carbon dioxide, it being a gas at the temperatures of technical interest (298 ≤...
Article
Full-text available
Supercritical fluids are used for the extraction of desired ingredients from natural materials, but also for the removal of undesired and harmful ingredients. In this paper, the pertinent physical and chemical properties of supercritical water, methanol, ethanol, carbon dioxide, and their mixtures are provided. The methodologies used with supercrit...
Chapter
Deep eutectic solvents have been used extensively for the extraction and separation of a great variety of substances from diverse media. Several review papers deal with the development of deep eutectic solvents for using them for extraction purposes (Pena-Pereira and Namiesnik in ChemSusChem 7:1784–1800, 2014 [1], Tang et al. in J Separ Sci 38:1053...
Chapter
The following definition is generally used in this book: deep eutectic solvents (DESs) are binary mixtures of definite composition of two components, one of which being ionic, that yield a liquid phase at ambient conditions, ≤25 °C. Some cases that do not conform to this restrictive definition are, however, also included, since they have properties...
Chapter
The trends regarding the chemical industry for the twenty-first century are along several paths (Sheldon in J R Soc Interface 13:116, 2016) [1]. One trend is the replacement of fossil raw materials (oil, natural gas) or mined minerals with renewable sources, such as biomass or recycled wastes. Sustainable processes for the valorization of waste bio...
Chapter
Since their advent in 2003, deep eutectic solvents have found applications in numerous fields where their properties as solvents, permitting the dissolutions of a large variety of solutes, and their being “green”, i.e., ecologically friendly as described in Chap. 1, gave them advantages over more conventional solvents. It is possible in the present...
Chapter
The practical application of deep eutectic solvents naturally depends on their properties, including their phase diagrams, thermodynamic properties, volumetric properties, transport properties, electrochemical properties, optical and spectroscopic properties, their chemical properties (polarity) and structures, and their toxicity and ecological beh...
Article
The calculation of standard absolute entropy values, S298o, of salt hydrates from their molecular volumes is reconsidered. The major effect on the entropy comes from the number of water molecules in the hydrated salt. Values of S298o for 12 salt hydrates and 9 anhydrous salts not previously reported are presented.
Article
Full-text available
The standard entropies S298°E of deep eutectic solvents (DESs), which are liquid binary mixtures of a hydrogen bond acceptor component and a hydrogen bod donor one, are calculated from their molecular volumes, derived from their densities or crystal structures. These values are compared with those of the components—pro-rated according to the DES co...
Article
The effect of ions on the structure of water in dilute solutions, whether they are structure-makers or structure-breakers, is manifested also in the volatility of the water. For more than 40 uni-univalent electrolytes, there is a linearly increasing relationship between 2φ(m = 0.4) − φ(m = 0.2), where φ is the osmotic coefficient and m is the molal...
Article
Ethanol pressurized at elevated temperatures in the subcritical state and at supercritical states has found uses in many processes, including fuel valorization and extraction of bioactive solutes from diverse sources. Therefore, its solubility parameters, both the total (Hildebrand) and partial (Hansen) parameters at the corresponding states are of...
Article
Full-text available
The critical temperatures of two dozen deep eutectic solvents, for only some of which these have been estimated previously, were estimated from the temperature dependences of their surface tensions and densities available in the literature according to the Eötvös and the Guggenheim expressions.
Article
The isothermal compressibilities, κT, and surface tensions, σ of room temperature ionic liquids (RTILs) were obtained from the literature. The products, κTσ were compared, in analogy with high-melting ionic liquids (molten salts) and liquid metals, with expectations from the scaled particle theory, the correlation lengths, and the dependence on the...
Article
Neoteric solvents for sustainable chemical processes are being continuously sought nowadays. Deep eutectic solvents (DES), i.e., liquids that are mixtures of two components that have freezing points considerably below the melting points of these components, constitute a possible solution for this search. Mixtures of certain congruently melting salt...
Article
Deep eutectic solvents (DES) are competitive solvents for the reversible capture of carbon dioxide and sulfur dioxide. They are ‘green’, i.e., friendly to the environment and inexpensive to produce. The solubilities of these gases in a variety of DES have been collected from the literature and reviewed and are described by means of the capacity (mo...
Article
Full-text available
The cohesive energies of room temperature ionic liquids, RTILs, at the reference temperature Tref = 298.15 K have been obtained from their molar enthalpies of vaporization. They are ce(298) = ∆vH°(298) − 298.15R, on regarding the vapors as single ion-paired molecules. The cohesive energy densities, ced = ce/V = δH²are the squares of the (Hildebrand...
Article
Full-text available
In this study, the anion-binding bis(cyclopeptide) 2 is introduced, which dissolves freely in water, affording up to 10 mM concentrations, thanks to triethylene glycol-derived substituents in the cyclopeptide subunits and the linker connecting them. Binding studies provided evidence that the anion affinity previously demonstrated for less-soluble a...
Article
Full-text available
The BET parameters r for the number of sites and ε for the excess molar enthalpy for adsorption of water on the salts, were obtained from their osmotic coefficients in concentrated aqueous salt solutions, as functions of their molalities, from the literature. The salts dealt with are those that form low melting eutectics with water that have not be...
Article
Following previous workers, the surface tension of room temperature ionic liquids (RTILs) is shown to depend reciprocally on the surface area of the void space in the RTILs. The void space in liquids in general and in RTILs in particular can be expressed in several manners. The fraction of free space in RTILs can be estimated well and most simply f...
Article
The cohesive energy densities ced and the internal pressures Pint of aqueous methanol mixtures are calculated from literature data for the entire composition range over the temperature range from 273 to 473 K, at saturation pressures up to 373 K and at 7.0 MPa above this temperature. The ratios Pint/ced are measures of the 'structuredness' of the s...
Article
The preferential solvation of many drugs in binary solvent mixtures, as derived by means of the quasi-lattice quasi-chemical and the inverse Kirkwood-Buff integrals methods from solubility and other thermodynamic data, is reviewed. The preferences were described in terms of the local mole fractions of the solvent components in the solvation sphere...
Article
Full-text available
The internal pressures, \(P_{\mathrm{int}}\), of practically all the liquid metallic elements in the periodic table up to plutonium (except highly radioactive ones) at their melting points were calculated from data in the literature. They are compared with the respective cohesive energy densities, ced, obtained from the literature data too. The rat...
Article
The relationship between the internal pressure Pint on the one hand and the cohesive energy density ced on the other and the ratio of the surface tension to the cube root of the molar volume σ/V1/3 (also called the Gordon parameter) was examined for a large number of liquids. These consisted of four classes: molecular liquids, liquid metals, room t...
Article
The diminution of the mean molar volume on electrostriction, ∆elVS, in the large electrical field of ions solvated by several solvents that are useful for the dissolution of electrolytes is presented. The solvents dealt with are ethanol, trifluoroethanol, 1,2- and 1,3-propanediols, glycerol, 2-butanone, 1,1- and 1,2-dichloroethane, pyridine, benzon...
Article
The adiabatic compressibilities κS of 64 liquid metallic elements at their melting points were obtained from the densities ρ and speeds of sound u reported in the literature. The isothermal compressibilities were obtained from the κS values by means of the molar volumes V, isobaric expansibilities αP, and isobaric molar heat capacities CP from the...
Article
Expressions for the composition dependence of the critical constants of mixtures or water and methanol are presented as are expressions of the vapor pressure, the molar enthalpy of vaporization, and the molar volume of methanol along its saturation curve. The internal pressure of saturated methanol is compared with it cohesive energy density, refle...
Article
The phenomena of electrolytes affecting the surface tension of aqueous solutions and producing measurable surface potentials are reviewed in the light of recent studies of them. The factual information presented includes the molar ionic surface tension increments ki = lim(ci → 0)(dσ / dci) of many ions and the surface potential increments ∆ χ = χE...
Article
In addition to the well-established Arrhenius-type temperature-dependence of the specific and molar conductivities of molten salts, it turns out that they also depend linearly on the molar volumes, in analogy with the behavior of their fluidities. Similar values of the molar volumes representing the immobilization of the ions result from both kinds...
Chapter
The properties of isolated ions, namely their molar masses and charges, the standard thermodynamics of their formation, their entropies and heat capacities, their magnetic susceptibilities, polarizabilities and softness are listed in tables. The sizes of ions are in fact relevant only in condensed phases (e.g., ionic liquids) and comprise their rad...
Chapter
Low-melting salts, i.e., those melting between 100 and 250 °C but are highly ionic are dealt with here. These include many inorganic salts as well as symmetrical quaternary ammonium and phosphonium salts, the properties of which as liquids are tabulated and discussed. Salt hydrates, whether melting congruently or not, form another category of low-m...
Chapter
Molten salts are characterized by their melting temperatures and where available their normal boiling points and critical points, all shown in tables. Structural aspects of molten salts as derived from diffraction measurements and computer simulations are tabulated and discussed. The thermochemical properties, as they are theoretically modelled, ar...
Chapter
Some salts, e.g., BeF2, ZnCl2, B2O3, SiO2, and GeO2, form glasses when sufficiently cooled. The glasses themselves are outside the scope of this book, but their properties as isotropic liquids are dealt with. Other high-melting salts (borates and silicates) are slags, and their properties as homogeneous liquids are dealt with here.
Article
The internal pressures, Pint, of two inorganic liquids: bromine and carbon disulfide were calculated from data in the literature and compared with their cohesive energy densities, ced. The values are in the ranges obtained for common organic liquids, but the ratio of ced/Pint for bromine is larger than might be expected for this non-polar but polar...
Article
A database for the solubilities of (volatile) liquid organic solutes in (non-volatile) room temperature ionic liquids at 298 K (or thereabouts) was constructed in terms of the infinite dilution activity coefficients, lnγi∞, from data in the literature. In most cases the fit of these data by the Hildebrand solubility parameter expression (Vi/RT)(δHi...
Article
Supercritical methanol (above 513 K and 8.1 MPa) is applicable to many processes, including biodiesel production from oils. Its total (Hildebrand) and the partial (Hansen) solubility parameters, the latter pertaining to dispersion, polarity, and hydrogen bonding interactions, are useful quantities, related to the solubilities of various solutes. Th...
Article
Full-text available
The solubility parameters, δH(Tb) , of nonreactive permanent gases at their boiling points Tb (<290 K) are calculated from individually discussed values of their molar enthalpies of vaporization and densities obtained from the literature. These values are tabulated and where available the coefficients of the temperature dependence expression δH(T)...
Article
Full-text available
The microscopic ionic volumes, v A, of complex inorganic anions, obtained from crystal unit cell volumes, as well as their standard molar volumes, \( V_{\text{A}}^{\infty } \), in aqueous solutions serve to establish whether these anions are water-structure-breakers or -makers. This is done via correlations with well known criteria for such effects...
Article
A large set of ionic volumes of the constituent ions of a variety of (non-protic) RTILs is used for the estimation of their molar volumes, hence their densities, at various temperatures by means of two fitting parameters only. The difference between the sum of the ionic volumes of the cation and the anion per mole and the actual molar volume is asc...
Chapter
The transfer of ions from a source solvent into a binary solvent mixture has been studied mainly for the cases where water is the source solvent and also one of the components of the solvent mixtures, that is, aqueous solvent mixtures. This chapter discusses the thermodynamic and transport properties of ions. It focuses mainly on binary solvent sys...
Article
Given the solubilities of non-ionic organic solutes in water, their solubilities in seawater are obtained by correlation expressions involving two descriptors for the constituent ions (or salts) of seawater and two descriptors of the solutes. The former are the standard partial molar volumes and the intrinsic molar volumes and the latter are the mo...
Article
Isothermal compressibility data of 23 aqueous electrolyte solutions at 25 ºC from the literature are used to calculate their hydration numbers, which diminish as the concentration increases. Their limit at very high concentration is near the 'number of adsorption sites' of water molecules on the ions, obtained by the BET method. On the contrary, hy...
Chapter
Hydrogen bonding (HB) in supercritical water (SCW) is much less extensive than in water at ambient conditions. Still, it plays an important role in the structural and dynamic properties of SCW and its capacity as a solvent. In order to deal with the HB it is necessary to have definite criteria that specify when a hydrogen bond exists or not, and th...
Article
The static (relative) permittivity of aqueous electrolyte solutions at 25 °C, ε(ω = 0) where ω is the frequency of the external field, has been obtained from the literature. The limiting dielectric decrements δ = − lim(c → 0)dε/dc, where c is the electrolyte concentration (≤ 1 mol·dm−3), are tabulated. The most appropriate additive individual ionic...
Article
The surface tensions σ of a large number of molten salts are known as (decreasing) linear functions of the temperature. They may be compared at a so-called “corresponding temperature”, of which 1.1Tm is a good choice (Tm/K is the melting temperature). It is shown that for highly ionic molten salts of the 1:1, 1:2, and 2:1 charge types σ is a linear...
Book
Over the past decade, numerous books have attempted to explain ions in aqueous solutions in relation to biophysical phenomena. Ions in Water and Biophysical Implications, from Chaos to Cosmos offers a physicochemical point of view of the spread of this matter and suggests innovative solutions that will challenge the biophysics research establishmen...
Article
Values of the adiabatic and isothermal compressibility, kappa(S) and kappa(T), of some 80 molten salts at the corresponding temperature of T = 1.1T(m) (T-m is the melting point) are obtained from literature data either directly or re-calculated here. For some of the series of salts: alkali metal halides and nitrates, divalent metal halides, and alk...
Article
Surface tension increments by aqueous electrolytes, kE = [γ(cE) - γ(W)]/cE, can be split into the ionic values, ki (kE = Σνiki), on an arbitrary but plausible manner, notwithstanding the effects of counter ions on the behavior of specific ions. Values for 41 ions, mono- and polyatomic and uni- and multivalent, are presented in conjunction with some...
Article
Binary liquid mixtures of acetonitrile (AN) and water (W) are widely used as reaction media in such fields of chemistry as physical organic chemistry, reverse phase liquid chromatography, and electrochemistry, among others. Much information on the structure of these systems and the interactions in them has accumulated since the author's often quote...
Chapter
Discover the many new and emerging applications of supercritical water as a green solvent. Drawing from thousands of original research articles, this book reviews and summarizes what is currently known about the properties and uses of supercritical water. In particular, it focuses on new and emerging applications of supercritical water as a green s...
Chapter
Various categories if ions are introduced, and the processes yielding ions in their isolated state (as an ideal gas): ionization and electron capture, as well as their relevant properties are presented. The properties of aqueous ions are dealt with on the basis of the restricted primitive model (point charge ions of given size in a continuum dielec...
Article
Water is a highly structured liquid, as indicated by its stiffness (cohesive energy density) and being ordered (large entropy of vaporization), its three-dimensional hydrogen-bonded network being its most outstanding feature. The extent of this network depends on the definition of the hydrogen bond, and both computer simulation and thermodynamic da...
Article
The recently published study of the solubility of ibuprofen (IBP) and naproxen (NAP) in aqueous 1,2-propanediol (PG) at several temperatures had as its purpose the modeling of the solubilities in terms of the solvent composition. It did not show how these drugs are preferentially solvated by water and by PG. The inverse Kirkwood-Buff integral (IKBI...
Article
The preferential solvation parameters, i.e., the differences between the local and bulk mole fractions of the solvents in solutions of certain drugs and polycyclic aromatic hydrocarbons (PAHs) are derived from their solubilities in binary solvent mixtures by means of the inverse Kirkwood-Buff integral (IKBI) and the quasi-lattice quasi-chemical (QL...
Article
Cryptand 222 (4,7,1 3,16,21,24-hexaoxa-1,10-diazabicyclo(8.8.8) hexacosane) is a well known sequestering agent for metal ions in solution. Thermodynamic data concerning the ligand itself and its metal complexes in various solvents enable the understanding of the ability of cryptand 222 to complex preferentially certain cations and of how solvents a...
Article
The Kirkwood–Buff integrals and the volume-corrected preferential solvation parameters for the first solvation shell of the completely miscible aqueous binary mixtures of 1,3-oxolane, γ-butyrolactone, diethylamine, 1,2-diaminoethane, pyrrolidine, morpholine, N-methylacetamide and N,N,N′,N′-tetramethylurea were calculated from thermodynamic data at...
Article
The Kirkwood Buff integrals and the volume-corrected preferential solvation parameters for the first solvation shell of the completely miscible aqueous binary mixtures of 1,3-oxolane, g butyrolactone, diethylamine, 1,2-diaminoethane, pyrrolidine, morpholine, N-methylacetamide and N,N,N',N'-tetramethylurea were calculated from thermodynamic data at...
Article
Stability constants and derived standard Gibbs energies, enthalpies, and entropies of complexation of a lower rim calix(4)arene ketone derivative, namely 5,11,17,23-tetra p-tert-butyl-25,26,27,28-tetra(benzoyl)methoxycalix(4)arene and the sodium cation in N, N-dimethylformamide/acetonitrile mixtures at 298.15 K are first reported. Stability constan...
Article
The most recent and comprehensive set of solubility data of C60 fullerene in various solvents at 298 and 303 K was treated by multivariate stepwise linear regression applied as the linear solvation energy approach. In a few cases where the fullerene formed crystalline solvates, the enthalpy of incongruent melting and the temperature of maximum solu...

Citations

... The cohesive energy density (CED) represents the total cohesion per volume of the liquid, and it occurs due to the intermolecular forces present within the liquid (Dack, 1975). The cohesive energy density (CED) (Dack, 1975;Almasi, 2020a;Marcus, 2020) has been evaluated using the energy of vaporization (ΔE vap ) and molar volume (V m ) given by the following equation: ...
... where x1 is the molar fraction of ethanol-free amygdalin, G1.3 and G2.3 are the Kirkwood-Buff integrals (cm 3 mol −1 ), and Vcor is the correlation volume (cm 3 mol −1 ). Thus, , and , are calculated as [63,64]: ...
... It has been reported that sCO 2 can also be used to remove micro pollutants or volatile organic compounds simultaneously along with the water removal 27 . Supercritical fluid extraction can be used for the extraction of desired or unwanted or harmful ingredients from various natural sources 28 . ...
... Deep eutectic solvents (DESs) are multicomponent mixtures prepared by combining hydrogen bond acceptors (HBAs) and hydrogen bond donors (HBDs), sometimes along with electrolytes at a particular eutectic molar ratio. [1][2][3][4] These systems are characterized by a pronounced depression of their melting point compared to their components and remain in the liquid phase over a wider temperature interval. 5 It is believed that the high entropy gain in liquid range is supported by strong H-bonding networks permeating the system, besides other specific interactions of the various components in DES. ...
... The surface tensions of DESs strongly depend on the intermolecular interaction between HBAs and HBDs, which forms a DES mixture. The DES surface tension varies with temperature, molar ratio, nature of HBAs/HBDs, and the alkyl chain length of the cation, as the alkyl chain length increases, the surface tension of DES decreases [60,84,93]. The hydrogen bond network can be disrupted by increasing organic salt, which leads to a decrease in the DESs surface tension [94]. ...
... Alternative solvents of extraction have been developed and studied over the years such as ionic liquids (ILs), 21 deep eutectic solvents (DES), 22,23 subcritical water (SCW), 24 supercritical CO 2 (SC-CO 2 ) 25 or solvent-free ( pressing, extrusion, ball milling, instant controlled drop pressure). 26,27 However, after extraction, deep eutectic solvent and ionic liquid extracts suffer from the impossibility to recover the solute by a simple evaporation of solvent. ...
... These bonds are most likely responsible for the large DES melting point depression compared to that of its individual components. 20 Because of its natural origin and low cost, choline chloride (ChCl) is widely used as a HBA component of many DESs. 15 As has been recently reported, 21,22 ChCl-based DESs are able to efficiently absorb ammonia. ...
... DESs are green and highly efficient solvents that are produced by mixing two or more components of hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) chemicals in an appropriate mole ratio to obtain an eutectic mixture [18]. DESs have several distinctive characteristics such as, thermal stability, low moisture sensitivity, low partial vapor pressure, ease of preparation, and ability to dissolve a wide range of materials both hydrophobic and hydrophilic [19,20]. We used DES (called DES-1) as an extractant as well as a coordination ligand for Hg (II). ...
... Undoubtedly, the knowledge of the mutual solubilities of water and ILs or CO2 solubility in ILs is of key importance as regards their applications as pure diluents in the chemical engineering field. 57,58 ILs turn out to be very normal organic diluents in which diversified chemical reactions could be accomplish. Such investigations are of interest to the field of metallic removal but also on a wider perspective, in order to predict their eco impact and to overcome their leaching drawback by adjusting their chemical composition. ...
... The crystal structures of some of the components, from which the molecular volumes are calculated as v m = v uc /Z, where v uc is the unit cell volume and Z the number of formula units per unit cell, are from [18][19][20][21][22][23][24]. In the cases of unconventional DESs based on salt hydrates and water as components [25], the standard molar entropy of the DES is calculated using Equations (1) and (2) as for the conventional ones, but for the solid hydrates the value of v mA is better obtained from the unit cell volumes of the crystalline salt hydrates per formula unit [26] rather than from the salt density. For the salt hydrate/water DESs the standard molar entropy of the hydrogen bond donor liquid water at 298.15 K is 69.91 J K −1 mol −1 [27]. ...