Dichlorocarbene and analogs: discovery,properties and reactions

Russian Chemical Bulletin - The discovery and studies of chemistry of dichlorocarbene and other electron deficient carbenes are discussed.     

Emulsion stability and potassium leakage in emulsion liquid membrane systems

Potassium leakage was studied in liquid membrane systems containing various emulsifiers and compared with emulsion, stability in the storage test. The effects of various parameters upon emulsion stability and the leakage of standard traces are discussed. The transfer of cations can be caused by emulsion breaking, by transport with the specific carrier and/or with surfactants used as emulsifiers. The latter case becomes especially important when hydrophilic surfactants, e.g. ones containing polyoxyethylene chains, are present in liquid membranes. In systems containing hydrophobic emulsifiers the transfer of potassium is relatively low. In each case considered the effect of emulsifiers upon the transfer of the standard tracer should be checked prior to using the leakage test to characterize emulsion stability.     

DTA determination of the anhydrite content in rock salts

The DTA method was used to determine the phase diagram of the NaCl-CaSO₄ system over the range 0.55 wt.% of CaSO₄ in air atmosphere. The effects of SiO₂, CaCO₃ and Fe₂O₃ on the melting temperatures of pure NaCl and the eutectic were determined. On the basis of the above temperatures, a method of quantitative determination of the anhydrite content in rock salts has been developed.

---

Zusammenfassung DTA wurde benutzt, um in Luft im Bereich 0 bis 55,0 Gew.% CaSO₄ das Phasendiagramm des Systemes NaCl-CaSO₄ zu bestimmen. Es wurde auch der Einfluß von SiO₂, CaCO₃ und Fe₂O₃ auf die Schmelztemperatur von reinem NaCl bzw. des Eutektikums bestimmt. Auf der Grundlage obiger Temperaturen wurde eine Methode zur quantitativen Bestimmung des Anhydritgehaltes in Steinsalzen entwickelt.

---

- 0–55,0 . , . , ( ) .

     

Extension of the measuring range of balances

The basic principle of comparing the sample mass with the mass of a reference body in equilibrium gives the equal-armed beam balance a unique accuracy. Main parameters characterising the suitability of the instrument are measuring range, resolution and relative sensitivity (resolution/maximum load). The historical development of the values of these parameters achieved depended strongly on the practical need in those times. Technically unfavourable scales of the oldest Egyptian dynasties (~3000 BC) could resolve mass differences of 1 g and had a relative sensitivity of at least 10^–3. More sophisticated instruments from the 18^th Dynasty (~1567–1320 BC) achieved a relative sensitivity of 10^–4 independent of the size of the instrument. In 350 BC Aristotle clarified the theory of the lever and at about 250 BC Archimedes used the balance for density determinations of solids. The masterpiece of a hydrological balance was Al Chazini’s 'Balance of Wisdom’ built about 1120. Its relative sensitivity was 2⋅10^–5. Real progress took place when scientists like Lavoisier (1743–1794) founded modern chemistry. At the end of the 19^th century metrological balances reached a relative sensitivity of 10^–9 with a maximum load of several kilogrammes. That seems to be the high end of sensitivity of the classical mechanical beam balance with knife edges. Improvements took place by electrodynamic compensation (Emich, Gast). In 1909 Ehrenhaft and Millikan could weigh particles of 10^–15 g by means of electrostatic suspension. In 1957 Sauerbrey invented the oscillating quartz crystal balance. By observing the frequency shift of oscillating carbon nanotubes or of silica nanorods, masses or mass changes in the attogram or zeptogram have been observed recently.     

Comments on surface structure analysis by water and nitrogen adsorption

Specific surface area and pore size distribution are determined usually from adsorption isotherms at low temperatures using nitrogen or noble gases. These are not absolute parameters and the measuring methods are fraught with serious difficulties. General problems of sorption measurements and recent developments are discussed. To obtain information for practical purposes these measurements need to be supplemented by investigations of the sorbate/sorbent system used in practice. Results of the measurement of nitrogen and water vapour adsorption on different materials are compared. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and characterization of metal polycarboxylates constructed from lanthanides(iii) and 1,2,4,5-benzenetetracarboxylic acid

The complexes of yttrium(III) and lanthanides(III) with 1,2,4,5-benzenetetracarboxylic acid were prepared as crystalline solids of the general formula Ln₄(C₁₀H₂O₈)₃⋅14H₂O. They are insoluble in water. On heating in air or inert gas atmosphere all compounds lose water molecules; next anhydrous compounds decompose to oxides. The yttrium complex and heavy lanthanide (from Ho to Lu) ones crystallize in monoclinic crystal system. The dehydration does not change the crystal structure of the compounds.     

Microsolvation of the [Ni(acac)(tmen)]+ complex

Microsolvation of the [Ni(acac)(tmen)]⁺ complex by a series of aliphatic n-alcohols (Solv) has been studied in ClCH₂CH₂Cl solutions by spectrophotometry. Based on the changes in the electronic spectrum of the afore-mentioned complex, observed under the influence of any alcohol, the equilibrium constants for the formation of the [Ni(acac)(tmen)Solv]⁺ and [Ni(acac)(tmen)Solv₂]⁺ species have been computed according to the algorithm presented in this work. It was found that, in all the systems studied, the stability of five-coordinated [Ni(acac)(tmen)Solv]⁺ is higher than that of octahedral [Ni(acac)(tmen)Solv₂]⁺. The resulting values are discussed in terms of the Lewis basicity of alcohols.     

Steam-carbon gasification catalyzed by calcium: Assessment of the porous structure of active carbons from plum stones and synthetic active carbons

A need for an elaboration of the methods for synthesis and characterization of activated carbons with a requisite porous structure has existed for a long time. One of the methods giving possibility for creating controlled mesopore and micropore structures deals with the steam gasification of various carbon materials. In this work the effects of calcium catalyst on the catalytic steam gasification of active carbons from plum stones and porous polymers are presented. Determination of micropores capacity and specific adsorption in mesopores have been performed by means of the _s method, but adsorption on the heterogeneous solids was described by the integral equation with various local isotherms. This equation has been solved by the regularization method. Based on this method the changes in structural parameters of active carbons depending on the amount of calcium catalyst were estimated.Nomenclature d width of slit-like micropore - F(x) distribution function of the half-width - p vapor pressure of sorbate - p/p _N relative pressure - PSAC Plum Stone Active Carbon - average pore radius, nm - S ₁ relative limit of the validity of experimental point on the adsorption isotherm in the computations by means of regularization method - SAC Synthetic Active Carbon - S _BET specific surface area calculated by means of BET method, m²/g - S _mes mesopore surface area, m²/g - S _mic micropore surface area, m²/g - T absolute temperature, K - V _mes sorption capacity of mesopores, cm³/g - V _mic sorption capacity of micropores, cm³/g - V _p sorption capacity of pores, cm³/g - w/w weight in weight concentration - x half-width of slit-like micropore, nm - x ₁ maximum of half-width of micropore slit, nm - average half-width of slit-like micropore, nm - X _min-X _max integration limits of thex Greek Letters Greek Letters variance of average half-width of slit-like micropore, nm² - local relative filling of micropores - total relative filling of micropores