Four sulphato and nitrato complexes of cerium(IV),viz. (NH4)4Ce(SO4)4·2H2O (1), (NH4)2Ce(SO4)3 (2), (NH4)2Ce(NO3)6 (3) and Cs2Ce(NO3)6 (4) were studied by simultaneous TG/DTA under various experimental conditions in order to establish their decomposition mechanism
and to compare the results with the literature data which have been reviewed. In the case of the ammonium compounds (1, 2 and3) the decompositions are accompanied by changes in the oxidation state of cerium; the presence of Ce(III) and Ce(IV) were
studied byex situ magnetic susceptibility and XPS measurements. The crystal structure of (1) was determined as well. It forms monoclinic crystals with space groupP21/c; the parameters of the unit cell are:a=12.638(18) Å,b=11.362(10) Å,c=13.607(11) Å, β=110.17(9)°,V=1834.05 Å3.
Stray neutron distribution in a medical cyclotron vault room was evaluated by neutron activation analysis (NAA). Neutrons
were generated in the production of radioactive nuclides, such as 18F, 11C, 13N and 15O, for diagnostic usage. Indium foil was adopted to evaluate the stray fast and thermal neutron intensity based on 115In(nf, n′)115mIn and 115In(nth, γ)116m1In reactions, respectively. The indium foils were weighed, sealed and placed at 62 points around the 6.7×8.2 m2 cyclotron room. Additionally, each indium foil was exposed for over 80 minutes during cyclotron operation and γ-peaks were
analyzed using an HPGe detector to evaluate the number of stray fast (Φf) or thermal (Φth) neutrons. The minimum to maximum numbers of fast and thermal neutrons were (3.47±0.11)×103 to (1.06±0.21)×104 n·cm−2·s−1 and 9 to 965 n·cm−2·s−1, respectively. The minimum detectable limit for stray neutrons was included herein to demonstrate the reliability. Accordingly,
60 and two points, respectively, the confidence level associated with the reported intensities of fast and thermal neutrons
reached 95%. The low qualified ratio in the evaluation of stray thermal neutrons might have been caused by either the high
Compton scattering plateau or the low intensity of the gamma-ray peak in the relevant spectrum.
Authors:M. Zielinski, G. Czarnota, and H. Papiernik-Zielinska
The13C kinetic isotope fractionation in the decarbonylation of lactic acid of natural isotopic composition by sulfuric acid has been studied in the temperature range of 20–80°C. The13C(1) isotope separation in the decarbonylation of lactic acid by concentrated sulfuric acid depends strongly on the temperature above 40°C. Below this temperature the13C isotope effect in the decarbonylation of lactic acid by concentrated sulfuric acid is normal similarly as has been found inthe decarbonylation of lactic [1-14C] acid. The experimental values of k(12C)/k(13C) ratios of isotopic rate constants for12C and13C are close to, but slightly higher than theoretical13C-kinetic isotope effects calculated (neglecting tunneling) under the asumption that the C(1)-OH bond is broken in the rate-controlling step of the dehydration reaction. Dilution of concentrated sulfuric acid with water up to 1.4 molar (H2O)/(H2SO4) ratio caused the increase of the13C isotope fractionation from 1.0273 found in concentrated sulfuric acid at 80.5°C to 1.0536±0.0008 (at 80.6°C). A discussion of the abnormally high temperature dependence of14C and13C isotope fractionation in this reaction and the discussion of the problem of relative14C/13C kinetic isotope effects is given.
Authors:F. Nazli Dınçer Kaya, Ingrid Svoboda, Orhan Atakol, Ümıt Ergun, Adnan Kenar, Musa Sari, and Kaan Emregül
Six nickel(II) complexes, using azide and thiocyanate ions, have been synthesized from bis-2,6(pyrazol-1-yl)pyridine (pp)
and some methyl derivatives, 2-(3,5-dimethyl(pyrazol-1-yl)-6-(pyrazol-1-yl)pyridine (app) and bis-2,6(3,5-dimethyl(pyrazol-1-yl)
pyridine (dmpp) in non-aqueous media. The complex structures were analyzed using elemental analysis, IR spectroscopy and thermogravimetry.
Appropriate crystals of complex, containing azide [Nipp(N3)2]·MeOH (I) and thiocyanate [Nidmpp(SCN)2·MeOH] (VI) were prepared and the molecular structures determined using X-ray diffraction. Complex I was seen to be dinuclear as stated in literature, space group P21/n, monoclinic, a=10.503, b=10.681, c=13.291 Å, β=106.56° and Z=2 whereas complex VI was found to be mononuclear, space group P21/n, monoclinic, a=8.646, b=12.614, c=20.697 Å, β=97.18° and Z=2. The Ni(II) coordination in both complexes were octahedral. Thermogravimetric studies showed azide containing structures
to resemble the characteristics of explosive materials. Coordinative MeOH were seen to leave the structure in thiocyanate
containing complexes, followed by irregular degradation above 300°C.
Authors:Margit Bán, Petra Bombicz, and J. Madarász
A new co-crystal of theophylline and phthalic acid with 1:1 molar ratio has been prepared. It crystallises in the monoclinic
crystal system, space group P21/c, a=11.5258(9), b=10.1405(6), c=13.9066(12) Å, β=106.827(4)°. The structure of the co-crystal has been revealed by single crystal X-ray diffraction. An infinite
helical polymeric chain is formed by intermolecular hydrogen bonds of the two neutral constituents. The hydroxyl group and
carbonyl oxygen atom in one of the carboxyl groups of phthalic acid form hydrogen bonds to O6 and to N(7)H atoms of theophylline,
respectively, while the other carboxyl OH group of phthalic acid is in hydrogen bond to N9 atom of theophylline by very strong
intermolecular interactions proven by 1883 cm−1 centred peak in FTIR spectrum.
Thermal degradation of this new supramolecular compound is a two-step process in air. At first phthalic acid (47.4%) released
up to 230°C, meanwhile it loses water and transforms into phthalic anhydride. In EGA-MS spectra, the characteristic fragments
of water (m/z=17, 18) appear from about 180°C, while absorption bands of phthalic anhydride are shown in EGA-FTIR spectrum at about 210°C.
In the second step theophylline begins to sublime, melts at 276°C, and then evaporates up to 315°C with minute residues.
Authors:Mohamed A. Zayed, M. F. Hawash, M. A. Fahmey, and Ali M. M. El-Gizouli
enantiomers obtained in MS/MS mode
The signal that appears at m/z = 206 (RI = 32.8%) refers to the appearance of the molecular ion [C13 H 18 O 2 ] + . The moderate intensity reflects the stability of the molecular
Authors:Mohammad Naderianfar, Majid Azizi, and Shapour Koohestani
MM . 2005 . Impact of Deficit Irrigation on Water Use Efficiency and Carbon Isotope Composition (Delta C-13) . of Field-Grown Grapevines under Mediterranean Climate . Journal of Experimental Botany 56 : 2163 – 2172 .