Dissociation of acetic acid in 50 mass % ethylene carbonate-water from 20 to 55°C

The dissociation constant of acetic acid in 50 mass % ethylene carbonate-water solvents has been determined at eight temperatures from 20 to 55°C by emf measurements of cells without liquid-junction containing hydrogen electrodes and silver-silver chloride electrodes. Acetic acid is weaker in the mixed solvent than in pure water. At 25°C, pK is 5.645 as compared with 4.756 in water, in spite of the fact that the dielectric constants of the two media do not differ materially. Standard changes in Gibbs energy, enthalpy, entropy, and heat capacity for the dissociation processes at 25°C were evaluated. The decrease in acidic strength when ethylene carbonate is added to the water medium appears to be largely the results of a destabilization of the two ionic species, especially a partial desolvation of the hydrogen ion.     

The effect of aqueous organic solvents on the dissociation constants and thermodynamic properties of alkanolamines

The dissociation constants of protonated monoethanolamine and N-methyldiethanolamine have been determined in methanol–water, ethanol–water, and t-butanol–water solvents. The alcohol mole fractions were ranging from 0.2 to 0.95 and the temperatures from 283 to 323 K, 283 to 333 K, and at 298.15 K, respective to the different solvents. The experimental results are reported with the standard state thermodynamic properties. The basic strength of the protonated alkanolamine decreases with decreasing dielectric constant and increasing temperature of the solvent.     

Polarizabilities and dipole moments of benzaldehyde, benzoic acid and oxalic acid in polar and nonpolar solvents

The purpose of this report is to calculate the orientation polarizability of benzaldehyde, benzoic acid and oxalic acid in polar and nonpolar solvents. The calculations are based on the knowledge of permanent dipole moment of the solutions. Other important physical quantities such as refractive index, density, specific volume, dielectric constant, molar polarization and molar refractivity are also calculated. Dipole moments of the solutions are calculated by using measured dielectric constants of the solutions. The dielectric constant measurements were made at 100 kHz. Relationships between the polarizability and concentration, specific volume, dielectric constant and dipole moment of the solutions are suggested.     

Effects of solvation on partition and dimerization of benzoic acid in mixed solvent systems

The partition of benzoic acid between 0.1M perchloric acid solution and two kinds of mixed solvents has been carried out at 25 degrees C. The partition and dimerization constants of benzoic acid have been determined in the 1-octanol-benzene and 2-octanone-benzene systems. In both the mixed solvent systems, with increasing content of 1-octanol and 2-octanone in each mixed solvent, the partition constant of benzoic acid has been found to increase, and the dimerization constant of benzoic acid in each organic phase to decrease. These phenomena are attributable to solvation of monomeric benzoic acid by 1-octanol and 2-octanone molecules in each mixed solvent.     

Electro-optical studies on synthetic polyelectrolytes—III: Electric birefringence of poly-n-alkyl-4-vinylpyridinium bromides in various solvents

The field strength dependences of the electric birefrigence of poly-N-butyl-4-vinylpyridinium (4-PVP · BuBr) samples have been measured in water and in various organic polar solvents. The observed change of sign of the birefringence, negative in water and positive in nitromethane, is explained by considering the respective influences of the intrinsic and form optical anisotropies. The lower degree of extension of the polyelectrolyte in some organic solvents is attributed to a lower degree of dissociation of the ionic sites. The influence of the dielectric constant and of the functional character of the solvent on the dissociation and solvation processes of the ionic sites is taken into account. Relaxation measurements in dimethylsulphoxide as a function of the molecular weight allow quantitative expression of the degrees of extension and of rigidity of the polyelectrolyte; the presence of aggregates has also been detected in DMSO solutions. A long alkyl chain, such as octyl, attached to the quaternary pyridinium groups strongly modifies the conformation of the polyelectrolyte and a polyelectrolyte-polysoap transition has been observed as a function of the solvent composition in water-ethanol mixtures.     

苯甲酸在醇-水混合物中溶解和离解的焓和熵

羟基化合物水溶液,尤其是一元醇与水的混合物在许多领域都有重要应用.其溶液性质常常显示出异常的特征,如粘度-组成曲线出现极大值[1]等.单靠氢键的概念已不能很好解释所观察到的许多特异性质.一般认为这类特殊性质来源于溶液结构.但到目前为止,对这类体系的结构性质的认识仍然比较模糊.焓、熵等热力学性质可以验证诸如用ＮＭＲ谱[2]、近红外差示光谱[3]等实验手段所得到的结果.实际上,热力学性质提供了一个简单可靠的结构“探针”[4,5].本文选择苯甲酸作为研究对象,测定它在乙醇水和异丙醇水两种混合溶剂中的溶解焓和离解焓,并结合文献报导…     

Spectrophotometric determination of the dissociation constants of methyl yellow in mixed protic solvents

The concentration dissociation constants (pK(a)) of methyl yellow, MY (H(+)In) in mixed aqueous solvents of methanol, ethanol, iso-propanol, tert-butanol have been accurately determined from spectrophotometric measurements at 25 degrees C and a constant ionic strength of 0.1 mol l(-1). It has been shown that in these solvents, the pK(a) values decrease with increasing composition of the organic co-solvent. A linear relationship between pK(a) and the mole fraction (x(2)) of the co-solvent was observed in a limited range of the compositions for each of the solvent systems. The results have been discussed in the light of transfer thermodynamic properties of the species existing in the dissociation equilibrium, solvent basicity and solute-solvent interactions. Furthermore, it was also observed that with the change of the solvents, the absorption spectra of MY shifted apparently and the color transition changed accordingly. The solvent effect on the spectra has been attributed to the isomerization equilibria of MY. A simple application of MY was also shown to the sodium acetate-hydrochloric acid titrations in the mixed solvents.     

Kinetics of reaction of triethylammonium carboxylates with ethyl α‐halogenoacetate in various solvents

The kinetics of the reaction of ethyl α‐halogenoacetate with benzoic acid in the presence of triethylamine in aqueous acetone and in various solvents have been investigated. The rate constant of the reaction is 4–260 times higher in aprotic dipolar solvents than in protic solvents. The simple regression and multiple regression of log k₂ with various solvent parameters have led to the conclusion that in addition to the solvent polarity, various other solvent properties, together or individually, influence the reaction rate. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 894–900, 1999     

Acid-base dissociation constants of 2,2'-bipyridyl in mixed protic solvents

The acid dissociation constants (K_a), base dissociation constants (K_b) and the autoprotolysis constants (K_s) for 2,2′-bipyridyl in water and in water+alcohol(methanol, ethanol, iso-propanol) mixed solvents have been determined at 25°C and an ionic strength of 0.1 mol l⁻¹, from a direct potentiometric method based on the treatment of the data of a single pH titration. It has been shown that K_a increases, whereas K_b and K_s decrease, with increasing proportion of the alcohol in the mixed solvents. Linear relations between pK_a, pK_b, pK_s and the mole fraction of the alcohol were observed in the composition range investigated. These results are discussed in terms of the properties of solvent and the interactions of the different species existing in dissociation equilibrium with solvents. It is concluded that the higher stabilization of both 2,2′-bipyridyl and its protonated form by dispersion forces and of the proton by its interaction with solvent molecules in the mixed solvents compared with that in water are largely responsible for the observed changes of pK_a with composition. On the other hand, the low stabilization of OH⁻ in the mixed solvents relative to that in water and the electrostatic effect are the main factors in determining the solvent effect on pK_b.     

Partition behaviour of benzoic acid in (water + n-dodecane) solutions at T = (293.15 and 298.15) K

The partition coefficients of benzoic acid in solutions of two immiscible solvents, water and n-dodecane, were measured at temperatures of (293.15 and 298.15) K. The experimental results indicated that at both temperatures the partition coefficients were not constant, but showed linear dependences on the concentration of benzoic acid in water. Dimerization of benzoic acid in n-dodecane and ionization in water were assumed based on the chemical theory and the experimental results verified this assumption quite well. Accordingly the association equilibrium constants of benzoic acid in n-dodecane were obtained by a linear regression. The regression results also showed that there was a very strong dimerization of benzoic acid in n-dodecane over the temperatures and concentration range investigated.     

Kinetic Studies of Block Polycondensation. I. Aggregation of Various Carboxylic Acids in Solvents of Low Dielectric Constant

Self-association of benzoic, octanoic, and octadecanoic acids was studied in solvents with a range of dielectric constants between 2.3 and 10. The number-average molecular weights were determined by means of vapor pressure measurements and were carried out at temperatures ranging from 25 to 90° C. It appears that, in these solvents of low dielectric constant, carboxylic acids are present mainly as molecular or ionic aggregates.     

Effect of water and organic solvents on the ionic dissociation of ionic liquids

The effect of water and several organic solvents on the density, viscosity, and conductivity of ionic liquids (ILs) 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), 1-n-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), and 1-n-butyl-3-methylimidazolium trifluoroacetate ([bmim][CF3CO2]) was studied at 298.15 K in wide composition ranges. The density, viscosity, and conductivity of the three neat ILs were also determined at various temperatures. Upon the basis of the molar conductivity of the mixtures and that of the neat ILs of the same viscosity, the degree of dissociation of ILs in the solutions was investigated. It can be deduced that the organic solvents enhance the ionic association of the ILs, the effect depending on the solvent dielectric constant, while water promotes dissociation significantly due to its high dielectric constant and its ability to form strong hydrogen bonds with the anions of the ILs.     

Potentiometric determination of the dissociation constants of L-histidine, proline and tryptophane in various hydroorganic media

The dissociation constant values of L-histidine, proline and tryptophane were determined at 25 +/- 0.1 degrees C by potentiometric pH titration in pure water and different hydroorganic solvent media. The organic solvents used were methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, acetone and dioxane. Initial estimates of the dissociation constant values of the different amino acids studied have been refined with ESAP2M computer program. It was observed that changing the medium permittivity as the solvent is enriched in methanol or ethanol has little influence on the pK*(a) values of the amino acids studied. The results obtained are discussed in terms of average macroscopic properties of the mixed solvents and the possible variation in microheterogeneity of the salvation shells around the solute.     

Empirical method for consideration of solvent effect on the dissociation constants of carboxylic acids

An empirical method was used to calculate 363 dissociation constants of 33 benzoic and acetic acid derivatives in 11 solvents. The relative error in the calculations did not exceed 9.5%, and the average error was no higher than 3%. The calculated values were compared with those obtained by quantum-chemical and other methods for determination of acid dissociation constants in different solvents.     

NMR Studies on the Effect of Solvents on the Dimerization of Benzoic Acid

The chemical shifts of carboxyl proton in benzoic acid have been measured in a variety of solvents. The characteristic monomer and dimer chemical shifts have been evaluated at 23°. A detailed discussion is given to illustrate the solvent shifts of carboxyl proton, from which the dielectric constant of solvent is considered as the main factor. The plot of carboxyl proton shift against (∈—1)/(∈+1) reveals a roughly linear dependence, indicating that a high field shift will be brought about by an increasing dielectric constant of solvent. Another linear relationship between log (δ—δ_D) and log ∈ suggests that an increase of ∈ will destroy the cyclic dimer, leading to an increase of the monomeric population and therefore to a higher field of the carboxyl proton signal.     

Dissociation constant of acetic acid in N-methylpropionamide from 5 to 55°C and related thermodynamic quantities

The dissociation constant of acetic acid in N-methylpropionamide (NMP) has been determined at 11 temperatures from 5 to 55°C by measurement of the electromotive force of cells without liquid junction containing hydrogen gas electrodes and silver-silver chloride electrodes. The pK at 25°C was found to be 7.995 (molal scale) as compared with 4.756 in water; thus, acetic acid is much weaker in NMP than in water despite the higher dielectric constant of the nonaqueous solvent (176 as compared with 78.3 at 25°C). The standard changes of enthalpy and entropy for the dissociation of acetic acid were calculated from the temperature coefficient of pK, and thermodynamic functions for the transfer dissociation process were obtained. The weakness of acetic acid in NMP is discussed in terms of electrostatic effects and solute-solvent interactions.     

Conductance of HCl,NaCl, Na acetate,and acetic acid in water-ethylene carbonate solvent mixtures at 25 and 40°C

The molar conductances of solutions of hydrochloric acid, sodium chloride, sodium acetate, and acetic acid were measured in water-ethylene carbonate (EC) solvent mixtures at 25 and 40°C. These solvents have dielectric constants higher than that of water. Four solvent compositions, in which the mole fraction (x ₂) of EC was 0.2, 0.4, 0.5, and 0.6, were studied at 25°C. For HCl and acetic acid at 40°C, additional measurements were made atx ₂=0.8 and 1.0. Analysis of the data by the Pitts equation was successful up tox ₂=0.6 and for HCl tox ₂=0.8. A graphical method, together with ₀ derived from the measurements for HCl, NaCl, and NaAc, yielded the dissociation constant of acetic acid up tox ₂=0.6. As EC is added, all the compounds studied displayed increased ion association. The acidic strength of acetic acid is greatly reduced; the dissociation constant atx ₂=0.6 is only 1/1000 that in water. The behavior of these electrolytes reflects the poor solvating power of EC, and the dielectric constant plays only a minor role.     

Subcritical water chromatography: A green approach to high-temperature liquid chromatography

At temperatures and pressures lower than 374 degrees C and 218 atm, subcritical water has widely tunable properties such as dielectric constant, surface tension, viscosity, and dissociation constant achieved by simply adjusting the temperature with a moderate pressure to keep water in the liquid state. At elevated temperatures, water acts like a weak polar organic solvent. Thus, subcritical water has been used as a green eluent to replace hazardous solvents commonly used as organic modifiers in RPLC. Subcritical water chromatography (SBWC) is capable of separating polar, moderately polar, and even some nonpolar analytes. Most of these low molecular weight solutes are stable at elevated temperatures during a chromatographic run. Some new packing materials are also quite stable and robust at mild temperatures ranging from 80 to 150 degrees C. Advantages of SBWC include the elimination of hazardous organic solvents used in traditional RPLC, rapid analysis time, improved selectivity, temperature-dependent separation efficiency, temperature-programmed elution, and compatibility with both gas- and liquid-phase detectors. In this paper, the technical aspects as well as the applications of SBWC are reviewed. Topics addressed in this review include the unique characteristics of subcritical water, analytes separated by SBWC, packing materials tested for SBWC, the application of GC and LC detection techniques in SBWC, SBWC instrumentation development, temperature effects on SBWC separation, and models developed for separation in SBWC.     

Potentiometric determination of successive stability constants of ethylenediamine complexes of several metals in dimethylsulphoxide

The stability constants of the complexes of silver(I), zinc(II), cadmium(II) and manganese(II) with ethylenediamine in dimethylsulphoxide at 25 degrees and ionic strength 0.1Mhave been determined potentiometrically. The stability constants are consistently larger in DMSO than in water as expected from the difference in dielectric constant for the two solvents.