Ionic Equilibria in Aqueous Solutions

2018 ◽  
pp. 217-238
Author(s):  
Franco Battaglia ◽  
Thomas F. George
Author(s):  
Nikolai F. Kizim ◽  
Anastasiya E. Tarasenkova

The extraction of phosphoric acid with a solution of tri-n-butyl phosphate (TBP) in toluene from its individual aqueous solutions in a concentration range of 0-11 M is investigated. The experiments are performed at room temperature (20 ± 1 °С). The isotherms of extraction of phosphoric acid under conditions of equality of the volumes of the saturating aqueous phase and the receiving organic phase are constructed. The extraction isotherm is nonlinear, but to an acid concentration in the aqueous phase of ~ 8 M, it is close to linear, and at higher concentrations, the amount of extracted acid increases harshly. To establish the mechanism of acid extraction in the system phosphoric acid – 0.1 M solution of TBP in toluene the method of combining a laboratory and computational experiment is proposed. The optimal parameters describing the extraction of phosphoric acid from natural aqueous solutions are determined. Calculations performed in two approximations were made. In the first approximation the condition of ideality of systems is accepted. In the second approximation the deviations of the properties of phosphoric acid solutions in aqueous solution are taken into account. For the two approximations the preferential extraction of phosphoric acid molecules in the form of H3PO4 ∙ nTBP type solvates (where n = 1, 3) is shown. In the range of concentrations of phosphoric acid in the aqueous phase from 6 to 11 M, the values of equilibrium constants are estimated, which describe the processes and reactions occurring in the system: stepwise dissociation of acid, distribution of TBP, formation of solvates of phosphoric acid, distribution of the resulting solvates of acid, displacement of ionic equilibria in aqueous phase. Mathematically these processes are taken into account using the law of mass action and the equations of material balance. It is believed that the system has established an equilibrium corresponding to a given temperature and pressure. The calculated values of solvate concentrations are in satisfactory agreement with experimental data.


1980 ◽  
Vol 58 (12) ◽  
pp. 1253-1257 ◽  
Author(s):  
Mian S. Sun ◽  
Donald K. Harriss ◽  
Vincent R. Magnuson

Activity corrections for ionic equilibria in aqueous solutions at 25 °C and ionic strengths up to 0.5 have been investigated. An empirical formula for activity corrections was generated by statistically fitting stability constant data for approximately 540 complexes, for which both thermodynamic and concentration stability constants were known, to a modified Debye – Hückel relationship. The general formula is[Formula: see text]χ > 0, where Δ log K is the difference in the logarithms of the stability constants at infinite dilution and finite I (I ≤ 0.5), and χ is an even integer dependent only on the stoichiometry and charge of the ions involved. Activity correction formulae for ionic equilibria involving classes of ligands (amino acid, inorganic, amine, and organic acid) also were developed. The general formula predicts stability constant corrections within 0.1 log unit for 87 % of the data used at ionic strength 0.1 and 64 % of the data at ionic strength 0.5. In addition, single ion activity coefficients as a function of ionic strength, 0 < I ≤ 0.5, are presented.


2008 ◽  
Vol 78 (4) ◽  
pp. 551-556 ◽  
Author(s):  
N. S. Kozhevnikova ◽  
A. A. Uritskaya ◽  
A. S. Vorokh ◽  
A. A. Rempel

Author(s):  
K. J. Böhm ◽  
a. E. Unger

During the last years it was shown that also by means of cryo-ultra-microtomy a good preservation of substructural details of biological material was possible. However the specimen generally was prefixed in these cases with aldehydes.Preparing ultrathin frozen sections of chemically non-prefixed material commonly was linked up to considerable technical and manual expense and the results were not always satisfying. Furthermore, it seems to be impossible to carry out cytochemical investigations by means of treating sections of unfixed biological material with aqueous solutions.We therefore tried to overcome these difficulties by preparing yeast cells (S. cerevisiae) in the following manner:


Author(s):  
S.A.C. Gould ◽  
B. Drake ◽  
C.B. Prater ◽  
A.L. Weisenhorn ◽  
S.M. Lindsay ◽  
...  

The atomic force microscope (AFM) is an instrument that can be used to image many samples of interest in biology and medicine. Images of polymerized amino acids, polyalanine and polyphenylalanine demonstrate the potential of the AFM for revealing the structure of molecules. Images of the protein fibrinogen which agree with TEM images demonstrate that the AFM can provide topographical data on larger molecules. Finally, images of DNA suggest the AFM may soon provide an easier and faster technique for DNA sequencing.The AFM consists of a microfabricated SiO2 triangular shaped cantilever with a diamond tip affixed at the elbow to act as a probe. The sample is mounted on a electronically driven piezoelectric crystal. It is then placed in contact with the tip and scanned. The topography of the surface causes minute deflections in the 100 μm long cantilever which are detected using an optical lever.


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