Search Results
Abstract
The adsorption heat of the stoichiometric displacement process for the adsorption of a solute in a liquid-solid system was investigated. On the basis of the SDM-A and the rule of the additivity of energy, an expression which describes the dependence of the adsorption enthalpy on the nature and concentration of the solute, and on the solvent and adsorbent, was derived. The adsorption heat determined for the solute with the traditional method can be divided into two independent fractions, relating to the adsorption of the solute and to the desorption of the solvent. Experimental data on both isotherms from the literatures and precise calorimetry were used to test the adsorption heat and its fractions computed quantitatively via the equations presented in this study, and a satisfactory degree of conformity between them was obtained.
Abstract
In order to reveal the reactivity of monosubstituted thiophenols, the hydrogen-isotope exchange reaction between T-labeled poly(vinyl alcohol) and each monosubstituted thiophenol (unlabeled) was studied in a liquid-solid system. Using both the data obtained and theA
-McKay plot method, the reaction was analyzed, and the rate constant (k) for the monosubstituted thiophenol has been obtained. Consequently, it has been found that (1) the higher the temperature is, the larger is the reactivity of monosubstituted thiophenols, (2) the temperature dependence of the effect of the substituent (in a monosubstituted thiophenol) on the reactivity of the monosubstituted thiophenol is weak, (3) the reactivity of monosubstituted thiophenols follows the Hammett rule, (4) the reactivity of monosubstituted thiophenols can be enhanced with one of the electron-attractive substituents.
Abstract
In order to reveal the reactivity of toluenethiols, the hydrogen isotope exchange reaction between one of three toluenethiols (o
–,m
–, andp
–) and poly (vinyl alcohol) labeled with tritium was observed at 50 
90°C. The reaction was analyzed with both the data obtained and theA
-McKay plot method, and the following has been quantitatively clarified: (1) the reactivity order of toluenethiols is (o
–>(m
–)>(p
–); (2) the temperature dependences of the reactivity of toluenethiols are nearly equal; (3) the reactivity of benzenethiol is considerably decreased by the CH3 group bonded to the ortho position.
Abstract
Both microcalorimetric determination of displacement adsorption enthalpies ΔH and measurement of adsorbed amounts of guanidine – denatured lysozyme (Lys) refolding on the surface of hydrophobic interaction chromatography (HIC) packings at 308 K were carried out and compared with that at 298 K. Study shows that both temperature and concentration of guanidine hydrochloride (GuHCl) affect the molecular mechanism of hydrophobic interaction of protein with adsorbent based on the analysis of dividing ΔH values into three kinds of enthalpy fractions. The adsorption in higher concentrations of GuHCl (>1.3 mol L–1) at 308 K is an enthalpy-driving process, and the adsorption under other GuHCl concentrations is an entropy-driving process. The fact that the Lys denatured by 1.8 mol L–1 GuHCl forms a relatively stable intermediate state under the studied conditions will not be changed by temperature.
Abstract
In order to reveal the effect of tritium (3H or T) on hydrogen isotope exchange, the exchange reaction between a certain compound (solid or liquid) and a tritiated one (gas or solid) was observed in gas-solid or liquid-solid systems. The reaction was analyzed using the data obtained and theA
-McKay plot method, and it has been quantitatively clarified that the effect of T on the reactivity of a material is changed with (1) the degree of polymerization of the material, (2) the kind of functional groups in the material, and (3) the reaction system.
Abstract
Thermogravimetry (TG) was successfully applied in order to study the heterogeneous properties of solid surfaces and adsorbed liquid films. The method utilized the thermogravimetric mass-loss Q-TG and differential Q-DTG curves with respect to temperature and time for the desorption of liquidus from solid surfaces under quasi-isothermal conditions. Evaluation of the experimental data revealed the heterogeneous properties of the tested samples. It appears that this modern special TG technique is very useful for the study of liquid/solid systems and can be competitive with traditional techniques because of the speed and accuracy with which the data are obtained and the simplicity of the experimental operations.
The paper presents possible applications of differential thermal analysis for study of the physicochemical properties of liquid/solid systems, mainly through programmable liquid thermodesorption from the sample under quasi-isothermal conditions. The results prove its applicability in the determination of solid physicochemical properties, and particularly in calculations of adsorption potential distribution, the activation energy of molecules adsorbed on the surface and the surface heterogeneity by means of computer techniques.
Abstract
A simple method has been adopted to obtain an important information on the heterogeneous properties of materials studied, adsorbed liquid films and liquid-solid interactions. The method utilizes Q-TG mass loss and the first derivative Q-DTG mass loss curves with respect to temperature and time obtained during programmed liquid thermodesorption in quasi-isothermal conditions. The values of the adsorption capacity, total porosity of material, the value of active centers, desorption energy distribution and mesopore-size distribution functions obtained by this method are in good agreement with those estimated on the basis of independent methods. The theoretical and experimental results provided novel and unique data on the heterogeneity of solid surfaces, properties of liquid adsorbed films and thermal stability of the liquid/solid interfaces. This paper presents the more important results obtained so far in the studies the liquid/solid systems by means of the Paulik's classical and quasi-isothermal techniques.
obtained without CO 2 , thus emphasizing the high stabilisation effect of the gas. Intermediate peaks denote the melting of metastable phases, which are very often formed in DSC experiments conducted on gas–liquid–solid systems due to the lack of stirring
organic and inorganic compounds, especially useful for the determination of liquid–liquid and liquid–solid systems. In this study, the molar enthalpies of dissolution of (1-C 8 H 20 NH 3 ) 2 CuCl 4 (s) at different concentrations are determined by an
