Limited stability of the pH reference material sodium tetraborate decahydrate (“borax”)

Thermogravimetric and X-ray powder diffraction analyses revealed that the pH reference material sodium tetraborate decahydrate (“borax”) is not a stable substance but, loosing some of its water of crystallization, transforms slowly into the pentahydrate. The connected pH changes of the solutions are opposite to and larger than, those expected according to the dilution value of the decahydrate as shown by differential potentiometric measurements. The transformation rate depends on the storing time in the closed original container, the time of and after the first exposure of the material to the atmosphere, the frequency of and the relative humidity during subsequent exposures, and the temperature. The transformation reaction is not understood in detail. However, the experiments showed that sodium tetraborate decahydrate is a reliable pH reference material, whose pH is constant within ΔpH=±0.005 within at least two years after preparation, even if occasionally exposed to the atmosphere. Further work will show whether this time limit can be somewhat extended.     

Benzenoid Molecules with Uniform Distribution of π-Electrons within Rings

In a recent work it was demonstrated that in linear hexagonal chains the distribution of π-electrons into rings (as computed by means of the Randić–Balaban method) is uniform, irrespective of the nature of the terminal fragments. We now establish that an analogous, yet somewhat more complex, uniformity in the π-electron distribution exists also in double linear hexagonal chains, as well as in some other benzenoid systems.     

Fluorescence quenching by excimer formation: quenching constant approximations for excimer formation-dissociation by classical potential models

Fluorescence quenching by excimer formation is studied on the assumption that the excimer formation and dissociation can be modeled as overdamped motion in an attractive potential (classical potential models). An approach to the zeroth-order, concentration-independent quenching constants is proposed which starts from a mean reaction-time ansatz and reduces the calculation essentially to the solution of the eigenvalue problem for the Smoluchowski operator which describes the excimer equilibration. For a square-well potential model it is shown that a quenching constant expansion in terms of relaxation modes, truncated at the kinetic level, gives a satisfactory approximation of the recently obtained exact zeroth-order result under defined conditions. It is demonstrated how this two-mode approach can be applied for a quenching constant estimation if the excimer formation and dissociation are modeled by more realistic interaction potentials, as for instance, Morse- or Gaussian-type ones.     

Fluorinated tellurium(IV) azides and their precursors

The perfluoroaryl tellurolates C₆F₅TeLi (1) and 4-CF₃C₆F₄TeLi (2) were prepared. These intermediates were identified by NMR spectroscopy and may form, depending on the reaction conditions, either the corresponding ditellanes C₆F₅TeTeC₆F₅ (3) and CF₃C₆F₄TeTeC₆F₄CF₃ (4) by subsequent oxidation, or in the case of 1, a telluranthrene (C₆F₄Te)₂ (5) by reaction with itself. The halogenation products of 5, ( C₆F₄Te)₂F₄ (6), (C₆F₄Te)₂Cl₄ (7), (C₆F₄Te)₂Br₄ (8), as well as the azidation product (C₆F₄Te)₂(N₃)₄ (9) were synthesized. Furthermore, in pursuit of our recent work on tellurium azides, the syntheses and properties of R₂Te(N₃)₂ (R=CF₃ (10), C₆F₂H₃ (11)) and RTe(N₃)₃ (R=CF₃ (12) and C₆F₅ (13)) are reported. The crystal structures of CF₃C₆F₄TeTeC₆F₄CF₃ (4), (C₆F₄Te)₂Br₄ (8), and (C₆F₂H₃)₂Te(N₃)₂ (11) were determined.     

Benzenoid Molecules with Uniform Distribution of π-Electrons within Rings

Summary. In a recent work it was demonstrated that in linear hexagonal chains the distribution of π-electrons into rings (as computed by means of the Randić–Balaban method) is uniform, irrespective of the nature of the terminal fragments. We now establish that an analogous, yet somewhat more complex, uniformity in the π-electron distribution exists also in double linear hexagonal chains, as well as in some other benzenoid systems.     

Perfluoralkyljod-verbindungen: Darstellungen und eigenschaften von CF3JO,CF3JOF2 und CF3JO2

Perfluoroalkyl iodine compounds: preparations and properties of CF₃IO, CF₃IOF₂, and CF₃IO₂. The trifluoromethyl iodine compounds CF₃IO, CF₃IOF₂, and CF₃IO₂ are formed from the reactions of CF₃I, CF₃IF₂ or CF₃IF₄ with ozone or silicon dioxide respectively. Their preparartions, properties, ¹⁹F-nmr spectra, and ir spectra are described.     

Perfluoralkyljod-verbindungen: das trifluormethyljod-bis-trifluoracetat CF3J(OCOCF3)2

CF₃I(OCOCF₃)₂ is formed from the reactions of CF₃IF₂ or CF₃IO with trifluoroacetic anhydride at low temperature. During the reaction of CF₃IF₂ with (CF₃CO)₂O CF₃IF(OCOCF₃) is formed as an intermediate product. The preparation, the ¹⁹F-nmr spectra and the thermal decomposition are described.     

Wärmekapazitätsmessungen Nach Scanning-Methoden Bis Zu Hohen Temperaturen

Scanning calorimetric methods permit determination of heat capacities at high temperatures up to 1600°C. For disk systems with power compensation application limits are in order of 700°C, and for cylindrical systems with electrical calibration up to 1000°C. For the high temperature range above 1000°C DSC plates and a cylindrical calorimetric systems based on the CALVET principle ('MULTI HTC’) are known. For cylindrical calorimetric systems the precision of the Cp data is between 2 and 5% even at high temperatures without any requirements on the kind and shape of samples. These results are better than data provided by DSC plate systems. This revised version was published online in July 2006 with corrections to the Cover Date.