Thermodynamics of formation of carnallite type double salts

The solubility of the systems RbCl–MgCl₂–H₂O, RbBr–MgBr₂–H₂O and CsBr–MgBr₂–H₂O have been investigated by the physicochemical analysis method at 25°C and formation of carnallite type double salts was established. The Pitzer model is used to calculate the thermodynamic functions needed to plot the solubility isotherms of the systems. The results obtained are in good agreement with the experimental data. The free energies of formation of carnallite and bromcarnallite type double salts from simple salts and the standard molar energies of formation are estimated.     

Investigation of the aqueous lithium and magnesium halide systems

The solubilities of the system LiBr–MgBr₂–H₂O have been investigated at 25°C and 50°C. It is established that the system is of a simple eutonic type. Pitzer's model is used for calculating the thermodynamic functions needed for plotting the solubility isotherms of the systems LiX–MgX₂–H₂O (X=Cl, Br) at 25°C. According to calculations made, the Gibbs energy of formation of LiCl·MgCl₂·7H₂O from simple salts is _rG°_m=–2.01 kJ-mol^–1, while the value _fG°_m=–2748 kJ-mol^–1 corresponds to formation from the elements.     

Thermodynamic simulation of four-component carnallite type systems

Summary The standard method ofPitzer for predicting the solubility isotherms of systems in which solid phases with a constant composition crystallize is applied to cases when mixed crystals are formed. The four-component carnallite type systems RbCl-CsCl-MgCl₂-H₂O, RbCl-KCl-MgCl₂-H₂O, and RbCl-RbBr-MgCl₂-MgBr₂-H₂O and the corresponding subsystems are thermodynamically simulated at 25°C. It is established that the solubility diagrams consist of crystallization regions of the simple saltsMX,MX, MgX ₂·6H₂O, and MgX₂·6H₂O and of the corresponding carnallite type double salts with the composition 1:1:6. A method of calculation of the integralGibbs energy of mixingG ^mix(s) of crystals formed in water-salt systems has been proposed. The results on the systems RbCl-KCl-H₂O, RbCl-RbBr-H₂O, and MgCl₂-MgBr₂-H₂O are compared with experimental data from the literature and with values calculated using various models.

---

Thermodynamische Simulation von Vierkomponentensystemen des Carnallit-Types

Zusammenfassung DiePitzer-Methode zur Voraussage der Löslichkeitsisothermen in Mehrstoffsystemen, in welchen feste Phasen mit konstanter Zusammensetzung auskristallisieren, wurde auch für Fälle angewendet, bei denen sich Mischkristalle bilden. Die Vierstoffsysteme RbCl-CsCl-MgCl₂-H₂O, RbCl-KCl-MgCl₂-H₂O und RbCl-RbBr-MgCl₂-MgBr₂-H₂O, aus welchen Carnallit-Typ-Mischkristalle auskristallisieren, und die dazugehörigen Dreistoff-Randsysteme wurden bei 25°C simuliert. Man stellt fest, daß die Löslichkeitsdiagramme sowohl Kristallisationsbereiche der einfachen SalzeMX,M'X, MgX ₂·6H₂O und MgX ₂·6H₂O als auch der entsprechenden carnallitartigen Doppelsalze mit der Zuzammensetzung 1:1:6 umfassen. Eine Methode zur Berechnung derGibbs-EnergieG ^mix(s) für die in Wasser-Salz-Systemen gebildeten Mischkristalle wird vorgeschlagen. Die für die Systeme RbCl-KCl-H₂O, RbCl-RbBr-H₂O und MgCl₂-MgBr₂-H₂O erhaltenen Ergebnisse werden mit experimentellen Literaturdaten und Resultaten von Berechnungen aufgrund verschiedener Modelle verglichen.

     

Formation of carnallite type double salts by grinding mixtures of magnesium and alkali halides with the same anions

The formation of carnallite type double salts by grinding mixtures of hydrated magnesium halide and alkali halides with the same anions was investigated by X-ray diffraction, infrared spectroscopy and thermal analysis. Carnallite (KMgCl₃·6H₂O), cesium-carnallite (CsMgCl₃·6H₂O), bromo-carnallite (KMgBr₃·6H₂O) and cesium-bromo-carnallite (CsMgBr₃·6H₂O) were formed by grinding mixtures of MgCl₂·6H₂O with KCl or CsCl and MgBr₂·6H₂O with KBr or CsBr, respectively. Hydrated solid solutions of magnesium in potassium or cesium halides were obtained from that portion of potassium and cesium halides which did not take part in the formation of the double salt.     

Double Salts Formation in the Systems MX–MeX 2–H2O (M=K,NH4, Rb,Cs; Me=Mg,Mn, Fe,Co, Ni,Cu; X=Cl,Br)

Monatshefte für Chemie - Chemical Monthly - ?The data available on the solubility phase diagrams and on the crystallization of chloride and bromide double salts in the systems...     

Effect of the reaction state on the polymerization of p-xylenesulfonium salts

1,4-Phenylenebis(methylene) sulfonium salts were polymerized under different conditions to yield p-xylylene sulfonium salt polyelectrolytes in a broad range of molecular weights. The aqueous reaction mixture formed a reversible gel at initial monomer concentrations higher than 1.0M, but at lower concentrations it remained as an emulsion until reaction completion. The effect of reaction time on intrinsic viscosities and polymer yields for both the emulsion and the gel state is discussed. The higher yields obtained when the reaction was carried out in the presence of a water-immiscible organic solvent were apparently due to the effect of this solvent on increasing the concentration of the reactive intermediate that led to the polyelectrolyte. Both the addition of an organic solvent and the variation of the initial monomer concentrations allowed some control over the molecular weight of the polyelectrolyte formed.     

还原温度对双介孔钴基催化剂费-托合成性能的影响

通过等体积浸渍法制备了双介孔钴基催化剂,采用XRD、BET、SEM、H₂-TPR等手段考察了催化剂的性质,并研究了还原温度对催化剂结构及费托合成催化性能的影响。结果表明,随着还原温度的提高,催化剂活性位增加,活性增加,但增加到一定程度后活性降低,而甲烷选择性随着还原温度的提高逐渐增加,这是反应过程中催化剂表面存在的钴氧化物,使得水煤气反应变得活跃,烃产物移向低碳烃。     

Effect of substituent distribution on water solubility of O-methylcellulose

The effect of substituent distribution on the water solubility of O-methylcellulose (MC) was re-examined to elucidate the lower limit of the degree of substitution (DS) in water-soluble MC. To this end, a series of 2,3-MCs which are regioselectively substituted at the C-2 and C-3 hydroxyl groups were prepared by homogeneous methylation. It was found that the lower limit for the DS value of water-soluble 2,3-MC was almost the same as that for MCs having even distributions of substituents along the cellulose chain as well as in the anhydroglucose units. This revised version was published online in August 2006 with corrections to the Cover Date.     

碱性热处理对豌豆蛋白结构及溶解性的影响

本文研究了碱性热处理(pH 12+60℃)对豌豆蛋白结构及溶解性的影响.单独碱处理(pH 12)和碱性热处理均不能改变豌豆蛋白的亚级结构,但圆二色谱和内源荧光结果显示两种处理方法能够引起豌豆蛋白的二级和三级结构发生变化.相比单独碱处理,碱性热处理能够更加显著地使豌豆蛋白的折叠结构展开,使原来埋于内部的疏水基团暴露出来,...     

Air stable liquid clathrates: Solid state structure and hydrocarbon solubility of organic cation triiodide salts

A series of air and water stable organic cation triiodide salts have been prepared and characterized. Almost all of the salts isolated sustain liquid clathrate phases in the presence of benzene or toluene, the compositions of which were determined via¹H NMR spectroscopy. Two of the salts were also characterized via X-ray crystallography in order to determine the nature of any solid state interionic interactions (1-ethylpyridinium triiodide, monoclinic,P2₁/c,a = 9.6031(7),b = 15.129(3),c = 8.8160(16) Å, = 104.192(11)°,Z = 4,R = 0.041 for 2463 independent observed reflections; 1,2,4-trimethylpyridinium triiodide, orthorhombic,Pbcm,a = 9.434(4), 20.176(4), 7.411(4) Å,Z = 4,R = 0.045 for 966 observed reflections).     

Improving the solubility of berberine

A possible solution for improving the water solubility of berberine by the formation of multicomponent pharmaceutical salts provides the background for this commentary.     

Effect of polymer microstructure on solubility characteristics and interactions

The effect of polymer microstructure on the solubility characteristics and propensity for interactions of polybutadiene (PBD) has been studied by means of the general solvation equation using data reported by Alessi et al. An increase in the vinyl content from 8% to 69% did not affect the propensity of PBD to interact with and n electron pairs and with dipolar — polarisable probes. In contrast, the hydrogen-bond basicity decreased due to steric hindrance from the alkene side group.     

Effect of bromide salts on cationic micellar catalysis

 The effect of bromide salts, MBr [M=Na, (CH₃)₄N, (C₂H₅)₄N, (C₄H₉)₄N, C₈H₁₇N(CH₃)₃], on the first-order rate constant, k ₁, of basic hydrolysis of 2,4-dinitrochlorobenzene in micelle solutions of cetyltrimethylammonium bromide has been studied. The main results are as follows. The molar ratio concentrations of OH⁻, m ^S _OH, on the micelle surface in the presence of different concentrations of Br⁻ ions, were calculated on the basis of the pseudophase ion-exchange model, and there is a linear relation between k ₁ and m ^S _OH. The relation between k ₁ and the concentrations of various bromides could be presented with a single curve, and the cations of the bromides have little effect on k ₁. Under the experimental conditions, there is a linear relation between 1/k ₁ and the concentrations of Br⁻; thereby a new method calculating the competition binding constant between OH⁻ and Br⁻ from dynamic data is proposed. The hydrodynamic radii of the micelles increase with the addition of bromide salts. Received: 1 August 2000 Accepted: 31 January 2001     

Effect of organic salts on micellar growth and structure studied by rheology

We report a rheological study on the effect of adding organic salts [sodium tosylate (NaTos) and benzoic acid potassium salt (BaPs)] on the micellar growth and structure of aqueous solutions of cethyltrimethylammonium chloride (CTAC) at a constant molar concentration ratio [salt]/[CTAC]. The rheological data show two well-defined domains of growth characterized by scaling laws for the surfactant concentration. The addition of NaTos leads to an unusual maximum in the viscosity-surfactant concentration curve. Before the maximum (domain 1), the analysis of the data (η₀, τ_R and G ₀) suggests the presence of branched micelles (connections). After the maximum (domain 2), however, the exponents of the scaling laws do not reflect either the relaxation of this branched structure or that of an entangled transient network structure. A faster mechanism of relaxation, not yet elucidated governs their dynamics. The exponents of the power laws in the presence of the BaPs are found, however, to be in accordance with the theory of equilibrium polymers. Received: 15 April 1998 Accepted in revised form: 20 October 1998     

Prediction of solubilities,the effect of temperature on the solubility of n‐alkanes,and the mobile order theory

The solubility equation derived from the thermodynamics of mobile order theory was used (1) to predict the solubility of three solid n‐alkanes—octadecane, dotriacontane, and hexatriacontane—in nonassociated and self‐associated liquids at 25 °C and (2) to predict the increased solubility in particular solvents with increasing temperatures. The evolution of the predicted solubility rested on the relative importance of the different terms contributing to the solubility. Generally, the fluidization of the solute presented a reluctance to the solubility. In nonassociated liquids, the balance of placing the entropy correction and the change in the nonspecific cohesion forces played up, whereas in the hydrogen‐bonded liquids, the solubility was determined by the hydrophobic effect. The effect of increasing the temperature of the dissolution of the solute was a reduction in the negative fluidization and nonspecific cohesion forces, which resulted in increased solubility. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 43–50, 2000     

Thermal decomposition of rhombohedral double carbonates of dolomite type

DTA and TG studies in air were carried out for hydrothermally prepared rhombohedral double carbonates of dolomite type, CaMg(CO₃)₂, CaMn(CO₃)₂, CdMg(CO₃)₂, CdMn(CO₃)₂ and CdZn(CO₃)₂. The solid decomposition products in air have been compared to those obtained under hydrothermal conditions with CO₂ pressure. The dolomite [CaMg(CO₃)₂] decomposes in two stages both in air as well as under high CO₂ pressure. The other carbonates studied, follow a single stage decomposition in air and a two stage decomposition under hydrothermal condition. In air, the manganese containing carbonates CaMn(CO₃)₂ and CdMn(CO₃)₂, decompose to form mixed oxides of CaMnO₃ and CdMnO₃ respectively, while CdMg(CO₃)₂ and CdZn(CO₃)₂ decompose to their respective two mono oxides.

---

Zusammenfassung Mittels DTA und TG in Luft werden die hydrothermisch hergestellten rhomboedrischen Doppelkarbonate (Dolomittyp) CaMg(CO₃)₂, CaMn(CO₃)₂, CdMg(CO₃)₂, CdMn(CO₃)₂ und CdZn(CO₃)₂ untersucht. Die in Luft erhaltenen festen Zersetzungsprodukte wurden mit denen verglichen, die unter hydrothermischen Bedingungen mit CO₂-Druck entstehen. Dolomit zersetzt sich sowohl in Luft als auch unter hohem CO₂-Druck in zwei Schritten. Die übrigen untersuchten Karbonate zersetzen sich in Luft in einem, unter hydrothermischen Bedingungen in zwei Schritten. In Luft zersetzen sich die magnesiumhaltigen Karbonate CaMn(CO₃)₂ und CdMn(CO₃)₂ unter Bildung der Mischoxide CaMnO₃ und CdMnO₃, während aus CdMg(CO₃)₂ und CdZn(CO₃)₂ jeweils die entsprechenden beiden Monoxide entstehen.

     

Effect of molecular symmetry on melting temperature and solubility

Molecular symmetry has a pronounced effect on the melting properties and solubility of organic compounds. As a general rule, symmetrical molecules in crystalline form have higher melting temperatures and exhibit lower solubilities compared with molecules of similar structure but with lower symmetry. Symmetry in a molecule imparts a positive amount of residual entropy in the solid phase (i.e., more possible arrangements leading to the same structure). This means that the entropy of a crystal of symmetric molecules is greater than the entropy of crystal of a similar, but non-symmetric molecule. An analysis is presented relating the enthalpy, entropy and temperature of melting for an idealised system of structural isomers of different molecular symmetries. The analysis presented helps explain why often, yet not always, the crystal of a more symmetric molecule, which has greater entropy to start (closer to that of the liquid), also exhibits a greater gain in entropy upon melting, compared with the crystal of a less symmetrical molecule. The residual entropy due to molecular symmetry has the direct effect of reducing the entropy gain upon melting (a negative effect). However, molecular symmetry also exerts indirect effects on both the entropy and enthalpy of melting. These indirect effects, imposed by the condition of equilibrium melting, are positive, such that it is the balance between the direct and indirect effects what determines the value observed for the entropy of melting of the symmetric molecules. When the indirect effect of molecular symmetry is greater than its direct effect, the observed entropy gain upon melting of the more symmetrical molecule is greater than that of a less symmetrical one.