Über die Wahl der Lösungsmittelsysteme bei der papierchromatographischen Trennung organischer Verbindungen

Zusammenfassung An praktischen Beispielen wurde gezeigt, in welcher Weise die Trennung organischer Verbindungen mittels Papierchromatographie erzielt werden kann. Man ist nicht auf einige bewährte Lösungsmittel systeme allein angewiesen, sondern kann von Fall zu Fall systematisch neue und geeignete Systeme benützen. Es hat sich bewährt, sich nach den elementaren Löslichkeitsregeln für organische Stoffe zu richten, unter der Voraussetzung, daß die zu chromatographierende Verbindung in der stationären Phase gut, in der mobilen Phase dagegen weniger löslich ist. Durch Änderung der stationären Phase (Wasser, nicht wäßriges, polares Lösungsmittel, nicht polares Lösungsmittel) oder der Polarität und Zusammensetzung der mobilen Phase kann man das Wandern der Flecke am Chromatogramm beeinflussen, beliebige R_fWerte erhalten und in vielen Fällen auch eine beliebige Reihenfolge der Verbindungen am Chromatogramm erzielen.Da die Löslichkeit organischer Verbindungen von intermolekularen Kräften abhängig ist, erscheint das Problem im Zusammenhang mit strukturellen Einflüssen sehr kompliziert und muß für jeden Fall auf eigene Weise gelöst werden. Die Löslichkeitseigenschaften können weiter durch Benutzung reaktiver Lösungsmittel beeinflußt werden, die z. B. die Verbindungen in wasserlösliche Salze überführen können. Dabei ist an die möglichen Komplikationen, die bei ionisierbaren Verbindungen durch Dissoziation und Hydrolyse entstehen können, zu achten.Von den Hauptfaktoren, die eine Trennung ermöglichen können, seien die folgenden erwähnt: funktionelle Gruppen, ihre Anzahl, Polarität, gegenseitige Stellung, bzw. ihre Basizität oder Azidität, C-Atomanzahl in homologen Verbindungen, inter- und intramolekulare Wasserstoffbindungen, sterische Faktoren u. a. Es ist dann von der Art des gewählten Lösungsmittelsystems abhängig, welche der genannten Faktoren im Vordergrund stehen und welche beseitigt werden.Wenn die Löslichkeitsunterschiede der zu trennenden Stoffe zu gering sind, um gute Trennungen zu ermöglichen, ist es zweckmäßig, die Verbindungen in solche Derivate zu überführen, deren Strukturunterschiede größer sind.

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Summary Practical examples are given to show how organic compounds can be separated by means of paper chromatography. The operator is not limited to tested solvent systems, but can use new suitable systems as the occasion demands. It has been found best to abide by the elementary rules of solubility of organic compounds, provided the compound to be chromatographed is quite soluble in the stationary phase but less soluble in the mobile phase. By altering the stationary phase (water, nonaqueous, polar solvent, non-polar solvent) or the polarity and composition of the mobile phase, the migration of the stains in the chromatogram can be influenced, selectedR _f -values can be obtained, and in many cases it is also possible to secure a desired succession of the compounds on the chromatogram.Since the solubility of organic compounds depends on intermolecular forces, the problem in connection with structural influences appears very complicated and must be solved individually for each case. Moreover, the solubility characteristics can be affected by using reactive solvents; for instance, the compounds can be converted into water soluble salts. Under such circumstances, sight must not be lost of the complications which may arise because of the dissociation and hydrolysis of ionizable compounds. The following are among the chief factors, which may make a separation possible: functional groups, their number, polarity, relative position, their basicity or acidity, C-atom number in homologous compounds, inter- and intramolecular hydrogen bonds, steric factors, etc. It then depends on the type of solvent system selected, which of these factors are predominant and which can be neglected or eliminated.If the solubility differences are too slight to permit good separations, the compounds to be separated should, if possible, be converted into derivatives whose structural differences are more pronounced.

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Résumé Des exemples pratiques montrent comment il est possible d'effectuer la séparation de combinaisons organiques par Chromatographie sur papier. Il n'est pas uniquement fait appel à des systèmes de solvants éprouvés mais, dans certains cas, de nouveaux systèmes appropriés sont systématiquement utilisés.Il s'est avéré satisfaisant de faire appel aux règles élémentaires de solubilité des substances organiques sous réserve que la combinaison à chromatographier soit suffisamment soluble dans la phase stationnaire et moins soluble dans la phase mobile. En faisant varier la phase stationnaire (eau, solvant non aqueux, solvant polaire, solvant non polaire) ou la polarité et la composition de la phase mobile, il est possible d'influencer la migration des taches du chromatogramme, d'obtenir des valeurs deR _f désirées et, dans de nombreux cas, d'obtenir les combinaisons dans un ordre déterminé sur le chromatogramme.La solubilité des combinaisons organiques étant fonction des forces intermoléculaires il en résulte que le problème se complique considérablement dans la mesure où l'on considère les influences structurelles et que chaque cas particulier doit recevoir une solution qui lui est propre. Les propriétés de solubilité peuvent en outre être influencées par l'emploi de solvants réactifs qui peuvent transformer, par exemple les combinaisons en sels solubles dans l'eau. Il faut alors tenir compte des possibilités de complications qui peuvent apparaître par dissociation et hydrolyse des combinaisons ionisables.Parmi les principaux facteurs qui permettent une séparation, il convient de mentionner les suivants: les groupes fonctionnels, leur nombre, leur polarité, leur position relative, ou encore leur acidité ou leur basicité, le nombre d'atomes de carbone de combinaisons homologues, les liaisons hydrogène inter- et intramoléculaires, les facteurs stériques, etc. Suivant la nature du système solvant choisi pourront alors varier les facteurs dont l'effet est prépondérant et ceux dont l'effet est nul. Lorsque les différences de solubilité des substances à séparer sont trop faibles pour permettre des séparations satisfaisantes, il est commode de transformer les combinaisons en dérivés dont les différences de structure soient plus importantes.

     

Some applications of the discrete fourier transform to problems of crystal lattice deformation II

The method elaborated in [1] is applied to the solution of some problems for a plane lattice and the linear chain. The method can be used to investigate deformations around crystal lattice defects.

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, [1] . .

     

Theory of tamm surface states in approximation higher than tight-binding approximation

The influence of the non-zero value of exchange integrals between Wannier functions, localized in non-neighbouring elementary cells (higher approximation than tight-binding), on the conditions of existence of Tamm surface states and the position of the energy level corresponding to the surface state is shown.

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, ( ) , .

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This paper is part of M. Tomáek's candidate's thesis.     

КРУЧЕНИЕ СТЕРЖНЕЙ С С ЕЧЕНИЕМ ФОРМЫ ПРЯМОУГОЛЬНИКА С ВЫР ЕЗОМ

[1] , 1) . [2].

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Twisting of notched rectangularly-shaped bars

It was pointed out in paper [1] that special cases of this solution are the problems of the torsion of a notched and unnotched rectangularly-shaped bar. Here, some results obtained earlier are generalized and in one concrete case very good agreement is obtained with the results of Sapondjan [2].

     

Bestätigung der Hertzschen Theorie mittels eine indirekte Methode

Ohne Zusammenfassung

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Wavelength distribution of X-rays in the focus of a monochromator and an estimate of the influence of this distribution on precision measurements of lattice constants

Wavelength distribution in the focus of a Johansson type monochromator is computed assuming the tube focus emissivityG(), reflection curveR() and wavelength distribution of the incident radiationJ(-₀) are known. It is shown e.g. that the centre of gravity may be shifted in accordance with the position of the crystal on the focal circle which may considerably influence precision measurements of lattice parameters.

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, G(,) R() J(-₀) . , , , .

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The author is grateful to Z. Hemanová for carrying out all the computations very carefully.     

Some applications of the discrete fourier transform to problems of crystal lattice deformation I

The theory of the discrete Fourier transform [1], [2] is applied in solving a system of difference equations describing the positions of atoms in a deformed crystal lattice. The crystal lattice is approximated by the Born-Kármán model modified to include the internal energy of the undeformed crystal.

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, , , [1] [2]. - , , .

     

The connection between low-gradient form of the positive column in oxygen and moving striations

The method of sliding photomultipliers was used to study the connection between two forms of the positive column in oxygen — the so-called low-gradientT-form and the highgradientH-form — and the presence of moving striations in the positive column. It was shown that in theT-form of a positive column striations are always present which move from the cathode to anode with a velocity of several thousand metres/sec. The highgradient form of theH-positive column, on the other hand, is not striated. The non-single-valuedness of the value of the longitudinal electric field in a discharge in oxygen is thus explained by the presence or absence of phenomena of a time variable character.

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— - H - — . , - , /. , , . , , , .

     

Rapid graphical determination of the radial intensity distribution of the small-angle scattering of X-rays from the measured data

The radially symmetrical small-angle scattering pattern (which would be obtained by the use of a direct beam having a point-like cross section) is in practice distorted, especially by the beam height. To eliminate this distortion the integration of a set of curves based on the derivative of the measured intensity distribution is required to derive the true radial intensity distribution. A rapid graphical method of plotting these curves is described and its accuracy is proved on an example. It is further shown that the radial intensity distribution can be determined in principle using the values of the measured curve instead of its derivative.

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( ) . , . . . , .

     

Theory of moving striations in plasma of D-C discharge I. Basic equation and its general solution

As a base for the theory of moving striations a partial integro-differential equation (26) is derived from the equations of continuity (1), (2), the Laplace-Poisson equation (3) and relation (4) between the electric field and the temperature of the electrons. Apart from the processes necessary for the actual formation of striations according to [1] and for the amplification of the wave of stratification according to [2], the equation also includes the processes defining the Debye length of the electrons, the influence of the axial electric field and of its local deflections on the motion of current carriers and the direct influence of the deviations in concentration of the electrons on the rate of production of current carriers. In deriving the equation the main attention is paid to the physical sense of the mathematical operations applied. The general solution is found by the method of the two-sided Laplace transformation and is described by triple integral convolution (42).

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I.

(1), (2), - (3) (4) (26). , , [1], , [2], , , . . (42).