Analysis of R. P. Smith's and D. C. Parris-R. B. Mclellan's carbon diffusivity data

A phenomenological model is proposed to account for the variation of carbon diffusivityD(N₁) with composition in austenite. This model is based on Parris-McLellan's statement that the increase ofD(N₁) with carbon concentrationN ₁ is due to the increase in chemical driving force. The gradient of the carbon activity in Wagner's and in Zupp-Stevenson's interpretation is presumed to be the intrinsic driving force. The predictions of the model are compared with carbonD(N₁) values both with [1] and without [5] a chemical concentration gradient. TheD(0) values and the carbon-carbon interaction coefficients ₁ are calculated by the use of the least squares method from the experimental data. The application of Zupp-Stevenson's definition of the activity coefficient ₁ results in a better fit of the theory to the experimental data.     

Interdiffusion in the Co-Ni system-I concentration penetration curves and interdiffusion coefficients

The interdiffusion in the Co-Ni system has been investigated in the temperature range of 950 to 1150 °C, by means of diffusion specimens of pure Co and Ni. The concentration curvesN(x, t) obtained with the aid of an JXA-3 A JEOL electron microprobe were evaluated using the smoothing cubic spline method by means of the Boltzmann-Matano equation. The obtained interdififusion coefficient values ¯D increase with the increasing Ni concentration and satisfy the Arrhenius equation at temperaturesH 990 °C. At lower temperatures the influence of high diffusivity paths may be effective, resulting in higher ¯D values. No expressive influence of atomic (Ni₃Co) or magnetic order on the interdiffusion has been detected. The activation enthalpyH values were found almost concentration independent. A Kirkendall effect study has been carried out with positive results which are presented in Part II of this paper. A new method for the determination of diffusants concentration in the Kirkendall plane was proposed. With the use of this method and of Darken equations the intrinsic diffusion coefficients were calculated. These results are given in Part III.     

Crystal packing of two 5‐substituted 2‐methyl‐4‐nitro‐1H‐imidazoles

Infinite chains connected by N—H...N hydrogen bonding form the primary packing motif in two closely related 4‐nitroimidazole derivatives, viz. 5‐bromo‐2‐methyl‐4‐nitro‐1H‐imidazole, C₄H₄BrN₃O₂, (I), and 2‐methyl‐4‐nitro‐1H‐imidazole‐5‐carbonitrile, C₅H₄N₄O₂, (II). These chains are almost identical, even though in (II) there are two symmetry‐independent molecules in the asymmetric unit. The differences appear in the interactions between the chains; in (I), there are strong C—Br...O halogen bonds, which connect the chains into a two‐dimensional grid, while in (II), the cyano group does not participate in specific interactions and the chains are only loosely connected into a three‐dimensional structure.     

Extraction of Am(III) in the presence of lanthanides and yttrium by benzyldimethyldodecylammonium nitrate from acidic nitrate solutions

We have investigated the effect of coextraction of lanthanides and yttrium on the distribution coefficients D_Am in the extraction of americium by benzyldimethyldodecylammonium nitrate (BDMLNNO₃) from nitrate solutions. In the coextraction of lanthanides, the extraction of Am(NO₃)₃ is suppressed, which is markedly manifested in the extraction of light lanthanides (La, Ce, Pr); of the series of lanthanides their extraction is the highest. The effect of nitric acid and the possibility of separation of lanthanides and americium by the application of three-stage multiple extraction is discussed.     

Electrosorption of hydrogen into palladium-gold alloys

Hydrogen electrosorption into Pd-Au alloys has been studied in acidic solutions (1 M H₂SO₄) using cyclic voltammetry. Pd-Au electrodes with limited volume were prepared by electrochemical co-deposition. It was found that the maximum H/(Pd+Au) ratios decrease monotonically with increasing gold content and reach zero at ca. 70 at% Au. Similarly to the case of Pd limited volume electrodes, two peaks in the hydrogen region, corresponding to two types of sorbed hydrogen, are observed on voltammograms for Pd-rich alloys. The hydrogen capacity, H/(Pd+Au), measured electrochemically, depends on the sweep rate in the cyclic voltammetry experiments, which suggests that two different mechanisms for hydrogen desorption from the Pd-Au alloy are possible. After a strong decrease of Pd concentration at the electrode surface, caused by long cyclic polarization to sufficiently anodic potentials, the amount of absorbed hydrogen is still significant for alloys initially rich in Pd. The results obtained from CO adsorption experiments suggest that only Pd atoms are active in the hydrogen absorption/desorption process. Electronic Publication     

Liquid chromatography of carbon clusters

Summary A comparison of three binary mobile phases in LC separation of C₆₀ and C₇₀ fullerences on chemically bonded 2,4-dinitroanilinopropyl (DNAP) stationary phase was carried out, n-Hexane-benzene has been found to be the best mobile phase for efficient separation of the all-carbon molecules permitting high loads in preparative LC.     

Stabilization of very rare tautomers of 1-methylcytosine by an excess electron

We characterized valence anionic states of 1-methylcytosine using various electronic structure methods. We found that the most stable valence anion is related to neither the canonical amino-oxo nor a rare imino-oxo tautomer, in which a proton is transferred from the N4 to N3 atom. Instead, it is related to an imino-oxo tautomer, in which the C5 atom is protonated. This anion is characterized by an electron vertical detachment energy (VDE) of 2.12 eV and it is more stable than the anion based on the canonical tautomer by 1.0 kcal/mol. The latter is characterized by a VDE of 0.31 eV. Another unusual low-lying imino-oxo tautomer with a VDE of 3.60 eV has the C6 atom protonated and is 3.6 kcal/mol less stable than the anion of the canonical tautomer. All these anionic states are adiabatically unbound with respect to the canonical amino-oxo neutral, with the instability of 5.8 kcal/mol for the most stable valence anion. The mechanism of formation of anionic tautomers with carbon atoms protonated may involve intermolecular proton transfer or dissociative electron attachment to the canonical neutral tautomer followed by a barrier-free attachment of a hydrogen atom to the C5 or C6 atom. The six-member ring structure of anionic tautomers with carbon atoms protonated is unstable upon an excess electron detachment. Indeed the neutral systems collapse without a barrier to a linear or a bicyclo structure, which might be viewed as lesions to DNA or RNA. Within the PCM hydration model, the anions become adiabatically bound with respect to the corresponding neutrals, and the two most stable tautomers have a carbon atom protonated.     

Low-temperature single crystal X-ray diffraction and high-pressure Raman studies on [(CH3)2NH2]2[SbCl5]

The structure of bis(dimethylammonium) pentachloroantimonate(III), [(CH₃)₂NH₂]₂[SbCl₅], BDP, was studied at 15 K and ambient pressure by single-crystal X-ray diffraction as well as at ambient temperature and high pressures up to 4.87(5) GPa by Raman spectroscopy. BDP crystallizes in the orthorhombic Pnma space group with a=8.4069(4), b=11.7973(7), c=14.8496(7) Å, and Z=4; R₁=0.0381, wR₂=0.0764. The structure consists of distorted [SbCl₆]³⁻ octahedra forming zig-zag [{SbCl₅}_n]²ⁿ⁻ chains that are cross-linked by dimethylammonium [(CH₃)₂NH₂]⁺ cations. The organic and inorganic substructures are bound together by the N-H…Cl hydrogen bonds. The distortions of [SbCl₆]³⁻ units increase, partly due to the influence of the hydrogen bonds which became stronger, with decreasing temperature. The preliminary room temperature, high-pressure X-ray diffraction experiments suggest that BDP undergoes a first-order phase transition below ca. 0.44(5) GPa that destroys single-crystal samples. The transition is accompanied by changes in the intensities and positions of the Raman lines below 400 cm⁻¹.     

Thin Films Deposition from Hexamethyldisiloxane and Hexamethyldisilazane under Dielectric-Barrier Discharge (DBD) Conditions

Hexamethyldisiloxane (HMDSO) and hexamethyldisilazane (HMDSN) were used as organosilicon reagents for PE-CVD of thin films under filamentary barrier-discharge conditions at atmospheric pressure. Efficient discharges were obtained in the region of moderate frequencies (5 kHz). The following mixtures of organosilicon reagents with carrier gas and oxidants or ammonia were investigated: HMDSO+Ar, HMDSO+N₂, HMDSO+O₂+Ar, HMDSO+N₂O+Ar, and HMDSN+NH₃+N₂. Under such conditions HMDSO was converted to produce thin films (10–1000 nm) of silicon oxide, generally containing admixtures of residual organic content (Si—CH_n and Si—H groups). The films deposited from HMDSN+NH₃+N₂ contained silicon, nitrogen and oxygen.     

Methyl 3‐(4‐methoxyphenyl)prop‐2‐enoate

The title mol­ecule, C₁₁H₁₂O₃, is almost planar, with an average deviation of the C and O atoms from the least‐squares plane of 0.146 (4) Å. The geometry about the C=C bond is trans. The phenyl ring and –COOCH₃ group are twisted with respect to the double bond by 9.3 (3) and 5.6 (5)°, respectively. The endocyclic angle at the junction of the propenoate group and the phenyl ring is decreased from 120° by 2.6 (2)°, whereas two neighbouring angles around the ring are increased by 2.3 (2) and 0.9 (2)°. This is probably associated with the charge‐transfer interaction of the phenyl ring and –COOCH₃ group through the C=C double bond. The mol­ecules are joined together through C—H?O hydrogen bonds between the methoxy and ester groups to form characteristic zigzag chains extended along the c axis.